CN105001661A - Metal polymer composite material with enhanced viscoelasticity and thermal performance - Google Patents

Metal polymer composite material with enhanced viscoelasticity and thermal performance Download PDF

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CN105001661A
CN105001661A CN201510266702.9A CN201510266702A CN105001661A CN 105001661 A CN105001661 A CN 105001661A CN 201510266702 A CN201510266702 A CN 201510266702A CN 105001661 A CN105001661 A CN 105001661A
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matrix material
stress
density
metallic particles
metal
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CN105001661B (en
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库尔特·E·海基莱
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Wild River Consulting Group LLC
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Abstract

The invention relates to a metal polymer composite material with enhanced viscoelasticity and thermal performance, and relates to a metal polymer composite material with enhanced or improved performance in composite materials. The performance includes elasticity, color, magnetism, heat conductivity, conductivity, density, improved extensibility, toughness, thermoplasticity or injection molding performance.

Description

There is the visco-elasticity of enhancing and the metal polymer composite of thermal characteristics
The divisional application that the application is the applying date is on February 9th, 2006, application number is 200680053915.2, denomination of invention is the Chinese patent application of " having the visco-elasticity of enhancing and the metal polymer composite of thermal characteristics ".
The application applies on February 9th, 2006 with applicant WildRiver Consulting Group as pct international patent, LLC (stateowned enterprise of the U.S., all designated states to except the U.S.) and applicant Kurt E.Heikkila (national of the United States, only to the U.S.) name submit to.
Technical field
The present invention relates to and there is the visco-elasticity of enhancing and the metal polymer composite of thermal characteristics.In described matrix material, described new capability is strengthened by the new interaction of component.Described metal polymer composite is not simple mixture, but obtaining excellent machinery, electricity and other performance by the unique combination of the metals like gold metal particles disperseed and polymer materials, wherein said unique combination optimizes the structure and characteristics of matrix material to obtain true composite property by the polymkeric substance of blended combination and metallic substance.
Background technology
A large amount of visual cognitive ability is had on the matrix material of special performance in creation.Be included in this type of material is have to improve the high density material of performance.Such as, lead is commonly used in needs in the application of high density material.The application of high density material comprises musket bullet, other ballistic projectile, bait, fishing pendant, wheel balancing block (weight) and other high-density applications.Due to resistance to α, β and gamma-radiation, EMI and the ductibility of lead, therefore lead is also used in the application of other performance needed except density, comprises and being used in radiation shielding.Plumbous snap on system processed fishes pendant to allow user to be pinched by fishing pendant like a cork on fishline without the need to instrument or without large difficulty.When musket bullet or other ballistic projectile, lead provides required density, penetration power and ductibility to obtain good precision and the wearing and tearing of minimum gun barrel.Lead be hunt and Military Application on main selection.As everyone knows, plumbous exist poisonous shortcoming on the terminal use of bullet and projectile.Increase due to lead concentration in lake and cause Natural Population dead, many jurisdiction of courts regions in the U.S. and other place have thought better of or have passed forbids selling and using plumb and plummet.There is workability, toxicity and radiation problem in the depleted uranium equally for projectile.
For many years, generally by two kinds of dissimilar combinations of materials are prepared matrix material with the advantageous property obtained from the two.True matrix material is unique, because the interaction of material provides the optimum performance of two kinds of components.Many kinds of matrix materials are known and are not simple mixtures.Usually, prior art thinks that the alloy that the metal combining some type with certain proportion is formed provides the special performance of metal/metal alloy material.Obtained metal/ceramic composite generally comprises combination metal-powder or fiber and can sinter the clay material of metal/ceramic composite into.
Usual combined thermoplastic or thermosetting polymer phase with strengthen powder or fiber, what produce certain limit is filled material, can form true polymers matrix material under appropriate condition.The filled polymer had as the additive of filler can not show composite property.Filler comprises the inorganic materials as pigment or extender for polymeric system usually.Usually obtained multiple fibre reinforced composites are with the fiber reinforcement performance of the mechanical property of polymkeric substance in unique matrix material that is improved.
A subclass of filled polymer material is wherein metallic substance, metallic particles or fiber dispersion metal-containing polymer mixture in the polymer.This type of material of great majority is mixture instead of true matrix material.Mixture usually easily can be separated into component and show the performance of component.True matrix material is resisted and is separated and shows strengthening the property of input material.True matrix material does not show the performance of each component.The U.S. Patent No. 3,895,143 of Tarlow teaches a kind of sheet material comprising elastomer latices, and described elastomer latices comprises inorganic fibre and the metallic particles of dispersion.The U.S. Patent No. 2,748,099 of the people such as Bruner teaches a kind of nylon material containing copper, aluminium or graphite, and described copper, aluminium or graphite are for changing the heat of material or electrical property instead of mixture density.The U.S. Patent No. 5,548,125 of the people such as Sandbank teaches a kind of clothes product comprising flexible polymer, and described polymkeric substance contains the tungsten of relative small volume percentage ratio, for acquisition radiation shielding.The U.S. Patent No. 5,237,930 of the people such as Belanger discloses containing copper powder and the dummy bomb of thermoplastic material being generally nylon material.The JP 63-273664 A of Epson Corporation discloses a kind of containing metal silicate fiber, the close polymeric amide knitting whisker and other material, as metallic matrix material.Finally, the U.S. Patent No. 6,048,379 and 6,517,774 of the people such as Bray discloses the trial of producing tungsten polymer composites.Which disclose the tungsten powder and the second optional bimodal polymers that polymkeric substance and particle diameter are less than 10 microns or steel fiber is combined as matrix material, to make high density material.These materials of prior art obtain the compound state of filled polymer, described filled polymer may have useful density but do not show allow to extrude, the visco-elasticity of injection moulding and other useful thermoforming production technique.
Although carried out a large amount of work about matrix material, not yet obtain density much larger than 10g/cm 3metal composite, its Midst density shows that the single of composite property is measured.The density increasing these materials will introduce unique mechanical property in matrix material, when deployed, obtain non-existent performance in compared with low-density composite.Need the material that there is high-density, hypotoxicity and there is improvement performance in electricity/magnetic property, ductibility, injection molding ability and visco-elasticity.
Summary of the invention
The present invention relates to and a kind ofly relative to prior art material, there is the thermal characteristics of improvement and visco-elasticity or manufacture the metal polymer composite of character.By selecting metal size distribution, polymkeric substance and processing conditions, the density that material of the present invention is improved by making the excluded volume of polymer-filled in matrix material minimize or other performance also obtain useful visco-elasticity.Gained matrix material is better than prior art matrix material at the visco-elasticity (as tensile modulus, storage modulus, elastic-plastic distortion etc.) of the toughness of the ductibility of the toxicity of density, reduction, improvement, improvement, improvement, electricity/magnetic property and machine molding aspect of performance.We find, and density and the polymer viscoelastic with elongation measurement are the useful performance of true matrix material in this technology and useful Prediction Parameters.When producing useful strengthening the property, the performance that the selection of the metallic particles of the accumulation of selected particle diameter and distribution and particle or mixing will be enhanced.The density obtained like this can be used as the predictive factors of other useful performance enhancement.The performance of material behavior utilization and improvement that the use also comprising the matrix material of interface modifier shows improvement is as elongation and other characteristic.The polymkeric substance that preferred matrix material can have a given molecular weight distribution with one or more of and the one or more of metallic particles with given distribution combine to obtain unique matrix material.Described material can be better than prior art matrix material at the ductibility of the toxicity of density, reduction, improvement, the toughness of improvement, the visco-elasticity of improvement and machine molding aspect of performance.We have prepared true matrix material and can obtain visco-elasticity.We have prepared matrix material by using interface modifier to improve the combination of particle and polymkeric substance.We have found that matrix material of the present invention can obtain the density of design level, mechanical property, thermal characteristics or electricity/magnetic property by careful blend composition.New viscoelastic property makes this material can be used for the multiple purposes that matrix material performs and providing of can't help easily to manufacture and be shaped to the material of useful shape.The packing material of prior art does not have these characteristics, will show fragility and physical disturbance when pressurized.
In one embodiment of the invention, the selected metallic particles selecting there is specified particle diameter and size distribution and the matrix material there is polymer formation that certain molecular weight distributes improving.This particle can have the circularity of restriction, and it promotes maximum property development.In this system, the matrix material of metallic particles and fluoropolymer realizes described performance.
High density material of the present invention can contain the pigment of interface modification or the composition of other improvement material visual appearance.The metallic particles mixed, bimetal (such as WC) or alloyed metal matrix material can be used for regulating the performance for specific end use.These performances include but not limited to that density, thermal characteristics are if thermal conductivity, magnetic property, electrical property are as electroconductibility, color etc.The combination of these materials and material can be used as solid-state electrochemistry structure (such as battery) and semiconductor structure.The metal-containing polymer material of preferred higher density also can combine to obtain unique matrix material with one or more of polymkeric substance and one or more of metallic particles.Second metal can combine with high desnity metal.Matrix material can comprise the multiple different combination of metal and polymkeric substance.Metallic particles can contain the metallic particles of two kinds of different metals, and often kind of metal all has relatively high density.In another embodiment, metallic particles can comprise high desnity metal particle and the second metal.Other useful metal of the present disclosure relate to itself can not obtain in the composite being greater than 10 density but can on the whole for matrix material provides the metal of useful property.This characteristic can comprise electrical property, magnetic property, the physical properties comprising thermal conductivity, acoustic shielding etc.This bimetallic example includes but not limited to iron, copper, nickel, cobalt, bismuth, tin, cadmium and zinc.Material of the present invention allows design engineer to have adjustment matrix material with the handiness of applicable end-use, and except non-required, avoids using poisonous or radio active material.Plumbous or depleted uranium no longer needs, because can use densified composite of the present invention in its typically used.Needing to carry out in other application of some adjustment to toxicity or radiation level, matrix material of the present invention can successfully use to design the mode becoming material desired properties.
In brief, utilize technology of the present invention, metal polymer composite of the present invention can provide the polymer composites performance of enhancing.A kind of important material comprises density and is greater than 10g/cm 3or more, usually about 5 to 21g/cm 3, about 5 to 18g/cm 3, be greater than 11.7g/cm 3, be greater than 12.5g/cm 3or be greater than 16.0g/cm 3matrix material.Described matrix material comprises high desnity metal particle, polymkeric substance and optional interfacial modifier material.Composition of the present invention also can contain content other additive at least about 0.01-5 % by weight as sighting agent, fluorescent marker, dyestuff or pigment.Matrix material of the present invention comprises the metal (metal of 47-90 volume %) of about 75-99.9 % by weight in the composite, the polymkeric substance (polymkeric substance of 10-53 volume %) of 0.5-15 % by weight.In the disclosure, the key property that we rely on density can regulate in the composite as, but other useful property also can design and enters in matrix material.
The metal polymer composite that density improves is by prepare with under type: form matrix material, wherein may to pile up or tap density acquisition metallic particles and polymer phase substantially only occupy described particle completely minimizes excluded volume so that particle is the highest.Adopt metallic particles, pile up described particle and by described particle and just enough combination of polymers, the excluded volume only having particle be filled, thus the high-density of matrix material can be optimized.Metal absolute density is selected to be greater than about 5, to be usually greater than 16g/cm 3metal, its with select for the formation of matrix material and put forward highdensity combination of polymers.Because metallic particles and polymeric constituent density increase, therefore composite density increases.Final composite density controls by the deposition efficiency of metallic particles in matrix material and the associated efficiency of the non-duty gap of filling dense packing particle with high density polymer material to a great extent.We find, and described deposition efficiency and charging efficiency improve by carefully selecting particle shape, particle diameter and size distribution.Described particle should be greater than 10 microns (particle diameter is greater than about 10 microns and refers to that the particle of small portion is less than 10 microns, in fact, is less than 10 % by weight, is usually less than the particle of 5 % by weight and is less than 10 microns).The size distribution of metal should be wide, generally includes the particle of about 10 to 1000 microns.Size distribution should contain the particle of at least some (at least 5 % by weight) about 10 to 70 microns, described particle also should contain the particle that at least some (at least 5 % by weight) is greater than 70, about 70 to 250 microns, and optional described particle also can contain some particles at 500+ micrometer range containing the particle of (at least 5 % by weight) about 250 to 500 microns.This distribution can be normal state, Gauss, lognormality or asymmetric normal distribution, but must comprise required particle size range.True matrix material until performance is developed and density reaches certain level and obtains, shows to use the property development and high-density that promote that interface modifier that matrix material is formed causes strengthening by the polymkeric substance of carefully processing combination and polymer beads.
Matrix material is not simple mixtures.Matrix material is restricted to the composition that two or more materials adulterate mutually with various percentage composition, and wherein each component keeps its basic original performance.The controlled combination of independent material obtains the performance being better than its component.In simple mixtures, mixing material does not almost interact and does not almost have performance enhancement.One of selection material is to improve rigidity, intensity or density.Atom and molecule are by a large amount of mechanism and other atom or molecule Cheng Jian.Such key can occur between the electronic cloud of atom or molecular surface, comprises molecule-molecule interaction, atom-molecule interacts and atom-atom interacts.Each becomes key mechanism to relate to characteristic force between atom center and size, is also even like this in interaction of molecules.The importance of this linkage force is intensity, and bond strength is with the change in Distance geometry direction.Main power in this bonding comprises ionic linkage, covalent linkage and Van der Waals (VDW) type bonding.Ionic radius and ionic linkage occur in ionic species as Na +cl -, Li +f -in.This kind of ionic species forms ionic linkage in the heart in atom.This generic key is firmly, is usually substantially greater than 100KJ/mol, is often greater than 250KJ/mol.In addition, the interatomic distance of ionic radius tends to very little and is about covalent linkage is produced by the overlap of the electronic cloud around atom, between atom center, form direct covalent bonds.Covalent linkage intensity is quite large, roughly with ionic linkage quite and tend to have interatomic distance less a little.
Polytype Van der Waals force is different from covalent linkage and ionic linkage.These Van der Waals forces tend to as intermolecular forces, instead of the power between atom center.Van der Waals force is divided into the power of three types usually, comprises dipole-dipole force, London force and hydrogen bond.Dipole-dipole force is a kind of Van der Waals force temporarily or caused by permanent change due to the quantity of electric charge on molecule or distribution.
Chemical force and the summary that interacts
Interaction type Intensity Key characteristic Intensity proportional in
Covalent linkage Very strong Longer scope r -1
Ionic linkage Very strong Longer scope r -1
Ion-dipole By force Short scope r -2
VDW aDipole-dipole By force medium Short scope r -3
VDW aIon-induced dipole Weak Very short scope r -4
VDW aDipole-induced dipole Very weak Extremely short scope r -6
VDW aLondon dispersion force Very weak b Extremely short scope r -6
avan der Waals is abbreviated as " VDW ".
bincrease because VDW London force increase with size and molecular dimension is not limited, therefore these power can become quite large.But in general they are very weak.
Dipole structure is produced by the charge separation on molecule, produces positive terminal and in whole or in part negative electricity opposite end in whole or in part.This power is caused by the electrostatic interaction between the negative electricity of molecule and positive electricity region.Hydrogen bond is the dipole-dipole interaction between the electronegativity region in hydrogen atom and molecule, and described electronegativity region generally includes the position of oxygen, fluorine, nitrogen or other relative electronegativies (relative to H).These atoms obtain and cause the dipole negative charge with the dipole-dipole interaction of positively charged hydrogen atom.London force is present in the Van der Waals force between substantially nonpolar uncharged molecule.Although this power occurs in non-polar molecule, this power is due in molecule caused by electron motion.Due to the rapid movement in electronic cloud, when therefore causing the temporary transient change in molecular polarization when electron motion, although non-polar molecule obtains little significant instantaneous charge.These small charge fluctuation cause the dispersive part of Van der Waals force.
Due to the characteristic that dipole or molecular polarization fluctuate, make such VDW power tend to bonding strength less, be generally 50KJ/mol or following.In addition, the scope that this power becomes magnetism is also greater than in fact ionic linkage or covalent linkage, and tends to as about
In Van der Waals matrix material of the present invention, we have found that the unique combination of the different-grain diameter of metallic particles, metal component, interactional improvement between particle and polymkeric substance, cause producing unique Van der Waals key.Van der Waals force produces between the atoms metal/crystal in particle, and is produced by the combination of the particle diameter in metal/polymer composite material, polymkeric substance and interface modifier.In the past, the material being characterized by " matrix material " only comprises the polymkeric substance being filled with and not almost being with or without the interactional particle of Van der Waals between granular filler.In the present invention, the interaction between selected size distribution and the polymkeric substance of interface modification makes particle can obtain the intermolecular distance producing substantial Van der Waals bonding strength.Viscoelastic prior art material is not almost had to there is no true composite structure.This guides us to derive and there is no this intermolecular distance in the prior art.In above discussion, term " molecule " can be used to refer to metallic particles, comprise the particle of Metallic Solids or amorphous metal aggregate, the subunit of other molecule or atomic unit or metal or metal mixture.In matrix material of the present invention, Van der Waals force occurs between the atoms metal set of working using crystal or other atoms metal aggregate form as " molecule ".The feature of matrix material of the present invention is that matrix material has the intermolecular forces between metallic particles, described intermolecular forces in the scope of Van der Waals intensity, namely about 5 to about 30KJ/mol and key be of a size of matrix material of the present invention comprises metallic particles and polymkeric substance, wherein said metallic particles has certain particle size range, make the particle of about at least 5 % by weight be about 10-70 micron and the particle of about at least 5 % by weight is about 70-250 micron, have between the molecule of the adjacent particle of matrix material the Van der Waals dispersion bonding strength that is less than about 4kJ/mol and key size, or be less than the intensity peace treaty of about 2kJ/mol van der Waals key size.
In the composite, the strength and stiffness of toughener are usually much higher than matrix, and give matrix material by its good performance.Matrix contains toughener with orderly high-density mode.Because toughener is normally discontinuous, therefore matrix also contributes to shifting the load between toughener.Processing can contribute to mixing and filler metal toughener.In order to help mixing, interface modifier can help to overcome the power stoping matrix to form the matrix material phase of basic continous.The performance of matrix material produces by by utilizing carefully processing and manufacture combining closely of obtaining.We think that interface modifier is on particle, provide exterior coating to promote the organic materials of combining closely of polymkeric substance and particle.Minimum properties-correcting agent can be used, comprise about 0.005-3 % by weight or about 0.02-2 % by weight.
For this disclosure, term " metal " relates to oxidation state metal, described oxidation state is about 0, at the most 25 % by weight or about 0.001-10 % by weight as oxide compound or metal or nonmetallic impurity, be not combined with ion, covalency or chelating (coordination) agent.For the present invention, term " particle " is often referred to the material making product, and the particle diameter of this product is greater than 10 microns and the size distribution had comprises the particle of at least some 10-100 micron and 100-4000 micron.In stacking states, this particle has the excluded volume of about 5-53 volume %.In the present invention, in the metal blends with different chemical and physical property, particle can comprise two kinds, three kinds or more kind sources of particles.
Usually, matrix material of the present invention utilizes melt-processed to manufacture, and can also utilize melt-processed and for product shaping.Usually, in the manufacture of high density material of the present invention, by about 40-96 volume %, be usually the metallic particles of 50-95 volume % or 80-95 volume % under heat and temperature condition with about 4-60 volume %, be usually the typical thermoplastic polymers combination of materials of 5-50 volume % or 5-20 volume %, processing is until the density that material obtains is about 5-21g/cm 3or about 5-18g/cm 3, be often greater than 10g/cm 3, 11g/cm 3, be preferably greater than 12g/cm 3, more preferably greater than 16g/cm 3, show that true matrix material is formed.Typical elongation is at least 5%, at least about 10% be usually 5-250%.As selection, in the manufacture of material, metal or thermoplastic polymer can be blended with interface modifier, and the material melt-processable of this modification subsequently becomes described material.Once material obtains enough density, just available conventional machining techniques material is extruded into product or be extruded into pellet, fragment, disk or other be easy to the starting material of the material forms of processing.When utilizing matrix material of the present invention to manufacture useful product, usually can in extrusion equipment, the appropriate matrix material obtained be heated and be pressurizeed, in suitable physical configuration, be formed as the suitable shape with appropriate amount material subsequently.In suitable product design, in matrix material manufacture or manufacture course of products, pigment or other coloring material can be joined in processing units.An advantage of this material is can process inorganic dyestuff or pigment simultaneously, thus obtains just can obtaining material that is attractive or decorative appearance without the need to carrying out coated outside or applying.Pigment can be included in blend polymer, can be evenly distributed in whole material and can obtain can not cracked, the surface that abrades or lose its decorative appearance.A kind of pigment of particularly important comprises titanium dioxide (TiO 2).This material has no toxicity, is brilliant white particle, can easily combine with metallic particles and/or polymer composites, to increase the density of matrix material and to provide white color for final matrix material.
We also find two kinds, the blend of the metal of three kinds or more kind particle form can obtain important composite property from the blending metal polymer composite structures.Such as, tungsten mixture or other high desnity metal particle can with the radiation comprising low α, β or γ particulate forms is provided for metastable nontoxic tungsten material, desired low cytotoxicity, outward appearance change or second metal of additional properties of other advantageous property blended.An advantage of double metallic composite material obtains by carefully selecting to produce the ratio of the density be applicable to for specific end-use.Such as, can produce with such as fluoropolymer or fluoropolymer there is 11g/cm 3to 12.2g/cm 3the tantalum/composite tungsten material of theoretical density.As selection, for other application, can produce with fluoropolymer and can have about 12g/cm 3to about 13.2g/cm 3the iridium composite tungsten material of density.This type of matrix material various all can have unique or special performance.The working method of these matrix materials and material have unique ability and performance, and this matrix material is used as because fusing point and other processing difficulties do not utilize the inventive method just can not make the alloy composite materials of two kinds of different metals of alloy.
Accompanying drawing explanation
Fig. 1 is the moulded product or extruded product be made up of material of the present invention.This figure is an example of the structure that available various methods described herein obtain.Support is the example with the goods of flexible structure being obtained practicality by metal polymer composite of the present invention.
Fig. 2 A and 2B is the cross section of extruded product of the present invention.
Fig. 3 A and 3B is the two kinds of forms comprising the snap on system of matrix material of the present invention or the fishhook of molding fishing pendant.
Fig. 4 A and 4B is two kinds of forms of the wheel balancing block of automobile of the present invention or truck inflation tire.
Fig. 5-11 provides the adaptive data of character needed for display visco-elasticity of the present invention and described technology formation material.
Figure 12-20 shows the visco-elasticity of uniqueness of the present invention compared with previous Metallic-filled polymer composition and polymkeric substance self.
Figure 21 and 22 explains the uniqueness of the stress-strain(ed) curve of the performance of display tungsten of the present invention and stainless steel composite material.
Figure 23 and 24 is the magnification region of Figure 22.
Figure 25 illustrates the stress-strain(ed) curve of THV fluoropolymer.
Figure 26 and 27 shows that the filled polymer non-composite material of prior art is fragility and damages when applying minimum stress, and true matrix material of the present invention has the useful mechanical property had a wide reach.
Figure 29 illustrates global density containing the matrix material multiple of the present invention of different metal component and volume tamped density to 30.
Embodiment
The present invention relates to a kind of metal polymer composite relative to prior art material with the improvement of visco-elasticity and the thermal characteristics strengthened or improve.The metal composite of single metal and mixing can be made to be applicable to new capability, to comprise density, color, magnetic, thermal conductivity, electroconductibility and other physicals.The improvement of the improvement that the operation instruction material property also comprising the matrix material of interface modifier utilizes and performance.Preferred matrix material can combine with the one or more of metallic particles with given distribution with the one or more of polymkeric substance with given molecular weight distribution and obtain unique matrix material.The present invention relates to a class matrix material, it is characterized in that having and be better than plumbous density and ductibility but not there is intrinsic toxicity that is plumbous and other high density material.This material can be used for needing in high-density, ductibility, toughness, formability and viscoelastic application.The present invention especially provides high density material, this high density material comprises high desnity metal particle as tungsten, polymer phase and optional interface modifier, and described interface modifier allows polymkeric substance and metallic particles to interact form the matrix material with desired characteristic and degree of performance and reach maximum potential density.This material obtains and is comprising the physicals exceeding prior art material in density, storage modulus, color, magnetic, thermal conductivity, electroconductibility and other physicals improvement, unless and need in a particular application, otherwise there is no point other toxicity or the residual radiation feature of lead or depleted uranium.Material of the present invention allows design engineer to have adjustment matrix material with the handiness of applicable end-use to avoid using poisonous or radio active material, except non-required.Lead or depleted uranium is no longer needed in its typically used.
Composite material combination metallic particles of the present invention and polymer materials, described metallic particles reserves excluded volume in maximum tap density, described polymer materials occupies described excluded volume substantially, but no longer occupies more volume to obtain the density of the maximum possible of composite.Tap density (ASTM B527-93) relate to material stacking must have how good.Pile up the volume fraction affecting excluded volume and be included in density calculation.The multiple metallic particles with appropriate size and distribution all can use.The important parameter of metallic particles distribution comprises the fact that the metallic particles diameter that is no more than 5 % by weight is less than 10 microns.In addition, 10-100 micrometer range is interior, quite most particle drops in 100-250 micrometer range and quite most particle drops in 100-500 micrometer range to have quite most particle to drop in metallic particles distribution." quite major part " refers to the particle of at least 10 % by weight.This distribution can be normal distribution, Gaussian distribution, lognormal distribution or asymmetric normal distribution, but must comprise required particle size range.
The final densities of metal is at least 11g/cm 3, be preferably greater than 13g/cm 3, more preferably greater than 16g/cm 3, the density of polymkeric substance is at least 0.94g/cm 3, but density is greater than 1-1.4g/cm 3, be preferably greater than 1.6g/cm 3polymkeric substance for increase density and to obtain useful polymer composites useful.The tensile strength of matrix material is 0.2-60MPa, and storage modulus (G ') is about 1380 to about 14000MPa, preferably about 3450 to about 6000MPa, and tensile modulus is at least 0.2-200MPa.A key character of matrix material of the present invention is to there is elastic-plastic distortion and Poisson's ratio thereof.Matrix material display elastoplastic deformation of the present invention.Under the stress extended causing matrix material, described structure with elastic model distortion until reach capacity, afterwards structure with plasticity mode deformation until reach its limit and structural failure.This performance is expressed as elongation at break, and wherein material is reaching elastic limit and extend at least 5% or at least 10% before fracture under continuous stress under stress.The Poisson's ratio of preferred material is less than 0.5 usually, and preferably about 0.1 to about 0.5.
The feature of the particle of the substantially spherical of the preferred rule of the present invention limits by the circularity of particle and long-width ratio thereof.The long-width ratio of particle should be less than 1: 3, is often less than 1: 1.5 and should reflects almost circular cross section or spheroidal particle.The circularity of particle, circularity or roughness are measured by the microscopic inspection of particle, wherein can calculate the roughness metric of automatic or manual.In such measurement, the girth selecting the representativeness of particle to select, measures the area of particle cross section simultaneously.The circularity of particle calculates according to following formula:
Circularity=(girth) 2/ area.
The circularity of desirable spheroidal particle is characterized as about 12.6.This circularity feature be less than about 20, the non-dimensional parameter of Chang Weiyue 14-20 or 13-18.
Metallic particles in matrix material used in the present invention comprises tungsten, uranium, osmium, iridium, platinum, rhenium, gold, neptunium, plutonium and tantalum, and can containing the second metal as iron, copper, nickel, cobalt, tin, bismuth and zinc.Although an advantage is non-poison or nonradioactive material to be used as need substitute that is plumbous and depleted uranium place, when the purposes of material to expection does not have can use lead and uranium during disadvantageous effect yet.Another advantage of the present invention is that the metallic substance that two or more can be utilized can not to be formed naturally alloy produces bimetal or more metal composite.By carefully selecting the combination of metal or metal and polymkeric substance to regulate multiple performance, the toxicity of material and radioactivity can design on demand in material.These materials do not use as large metallic particles, and use usually used as little metallic particles, are often called metallic particles.This kind of particle has relatively little long-width ratio, and long-width ratio is less than about 1: 3 usually.Long-width ratio is normally defined the ratio of the overall dimension of particle and the minimum size of particle.Usually, spheroidal particle is preferred, but enough tap densities can be obtained by the relatively uniform particle in dense structure.
Composite material combination metallic particles of the present invention and polymer materials, described metallic particles reserves excluded volume in maximum tap density, described polymer materials occupies described excluded volume substantially, but no longer occupies more volumes to obtain the density of the maximum possible of composite.
Multiple high desnity metal all can use.The nucleidic mass of tungsten (W) is 183.84, and ordination number is 74, belongs to VIB (6) race.Naturally occurring isotropic substance is 180 (0.135%), 182 (26.4%), 183 (14.4%), 184 (30.6%), 186 (28.4%), artificial radioactive isotope be 173-179,181,185,187-189.Tungsten to be found by C.W.Scheele in 1781 and was separated by J.J. with F.de Elhuyar in 1783.As one of rare metal, it accounts for about 1.5ppm in the earth's crust.Main ore is wolframite [(Fe, Mn) WO 4] and sheelite [(CaWO 4)], be mainly present in China, Malaya, Mexico, Alaska, South America and Portugal.The sheelite of U.S.'s exploitation contains the WO of 0.4-1.0% 3.K.C.Li is shown in the description of sepn process, C.Y.Wang, Tungsten, A.C.S.Monograph Series no.94 (Reinhold, New York, 3rd ed., 1955) 113-269 page; G.D.Rieck, Tungsten and Its Compounds (Pergamon Press, New York, 1967) the 154th page.Summary: Parish, Advan.Inorg.Chem.Radiochem.9,315-354 (1966); Rollinson, " Chromium, Molybdenumand Tungsten ", Comprehensive Inorganic Chemistry the 3rd volume, J.C.Bailar, Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 623-624,742-769 page.Tungsten is that Steel Grey arrives tin white non-ferrous metal, and crystalline form is body-centered cubic structure.Its density is d 4 2018.7-19.3; Its hardness is 6.5-7.5, and fusing point is 3410 DEG C, and boiling point is 5900 DEG C, and specific heat (20 DEG C) is 0.032cal/g/ DEG C, and melting heat is 44cal/g, and vaporization heat is 1150cal/g, and resistivity (20 DEG C) is 5.5 μ Ω cm.Under normal temperature, tungsten is stablized but form trioxide under red heat in dry air, is dioxide not by aqueous corrosion but by steam oxidation.Granular tungsten can also can be slowly dissolved in molten potassium hydroxide or sodium carbonate under suitable condition in the presence of air in spontaneous combustion; Dissolve in the molten mixture of NaOH and nitrate.Tungsten is at room temperature corroded by fluorine; By chlorine corrosion at 250-300 DEG C, when there is not air, obtain hexachloride, when there is air, obtain trioxide and oxychloride.In short, fusing point is 3410 DEG C, and boiling point is 5900 DEG C, and density is d 4 2018.7-19.3.
The nucleidic mass of uranium (U) is 238.0289 (being characterized as naturally occurring mixture of isotopes), and ordination number is 92, does not have stable nuclide.Naturally occurring isotropic substance is 238 (99.275%), 235 (0.718%), 234 (0.005%); Artificial radioactive isotope is 226-233,236,237,239,240.Uranium accounts for about 2.1ppm in the earth's crust.The main uranium ore of commercial significance is had to be carnotite, uraninite, torbernite (tobernite) and lime-uranite.Commercially important mineral reserve are positioned at Canadian Elliot Lake-Blind River basin, the Rand goldfield in South Africa, the Colorado of the U.S. and the Utah State, Australia and French.M.H.Klaproth is seen, Chem.Ann.II, 387 (1789) from the discovery of uraninite.E.Peligot is shown in the preparation of this metal, C.R.Acad.Sci 12,735 (1841) and Idem, Ann.Chim.Phys.5,5 (1842).Preparation flow and the details of pure uranium metal are shown in Chem.Eng.62, No.10,113 (1955); The United States Patent (USP) 2,852,364 (authorizing U.S.A.E.C. in 1958) of Spedding etc.Summary: Mellor ' s Vol.XII, 1-138 (1932); C.D.Harrington, A.R.Ruehle, Uranium Production Technology (Van Nostrand, Princeton, 1959); E.H.P.Cordfunke, The Chemistry ofUranium (Elsevier, New York, 1969) the 2550th page; Numerical digit author at Handb.Exp.Pharmakol, in 36,3-306 (1973); " The Actinides ", ComprehensiveInorganic Chemistry the 5th volume, J.C.Bailar, Jr., et al., Eds. (PergamonPress, Oxford, 1973) passim; F.Weigel, Kirk-Othmer Encyclopedia ofChemical Technology the 23rd volume (Wiley-Interscience, New York, 3rd ed., 1983) 502-547 page; Idem, The Chemistry of the Actinide Elements the 1st volume, J.J.Katz et al., Eds. (Chapman and Hall, New York 1986) 169-442 page; J.C.Spirlet et al., Adv.Inorg.Chem.31,1-40 (1987).Summary about toxicology and healthy effect is shown in Toxicological Profile for Uranium (PB91-180471,1990) the 205th page.Uranium is silvery white, glossiness radioactive metal, and it has ductibility and toughness, tarnishes fast in atmosphere and forms black oxidation nitride layer.Vaporization heat is 446.7kJ/mol; Melting heat is 19.7kJ/mol; The heat of sublimation is 487.9kJ/mol.Granular uranium metal and some uranium compounds can spontaneous combustions can be quickly dissolved in the HCl aqueous solution in air or oxygen.Non-oxidizing acid such as sulfuric acid, phosphoric acid and hydrofluoric acid only react with uranium slowly; Nitric acid is with moderate rate dissolved uranium; The dissolving near-by explosion intensity of granular uranium in nitric acid.Uranium metal is to alkali inertia.In short, fusing point is 1132.8 ± 0.8 DEG C, and density is 19.07; D 18.11; D 18.06.
The nucleidic mass of osmium (O) is 190.23, and ordination number is 76, belongs to VIII (8) race.Naturally occurring isotropic substance is 184 (0.02%), 186 (1.6%), 187 (1.6%), 188 (13.3%), 189 (16.1%), 190 (26.4%), 192 (41.0%).Artificial radioactive isotope be 181-183,185,191,193-195.Osmium accounts for about 0.001ppm and finds in osirita ore and all platinum ores in the earth's crust.Tennant found osmium in 1804.Preparation is shown in Berzelius et al., (Mellor quotes), A Comprehensive Treatise on Inorganic and TheoreticalChemistry 15,6887 (1936).Summary: Gilchrist, Chem.Rev.32,277-372 (1943); Beamish et al., Rare Metals Handbook, C.A.Hampel, Ed. (Reinhold New York, 1956) 291-328 page; Griffith, Quart.Rev.19,254-273 (1965); Idem, The Chemistry of the Rarer Platinum Metals (JohnWiley, New York, 1967) 1-125 page; Livingstone, ComprehensiveInorganic Chemistry, the 3rd volume, J.C.Bailar, Jr.et al.Eds. (PergamonPress, Oxford, 1973) 1163-1189,1209-1233 page.Osmium is pearl opal, glossiness metal, has closely packed hexagonal structure.Density is d 4 2022.61, it is being considered to the highest element of density for a long time.X-ray data shows that its density is a little less than iridium, and fusing point is about 2700 DEG C, and boiling point is about 5500 DEG C, and density is d 4 2022.61, specific heat (0 DEG C) is 0.0309cal/g/ DEG C, and hardness is 7.0 (Mohs' hardness).Osmium is stable in freezing air, and granular osmium also can be become tetroxide by air slow oxidation even at normal temperatures.The chlorine corrosion that osmium is dried under being heated by fluorine burn into more than 100 DEG C, but do not corroded by bromine or iodine.Osmium is corroded through long-time by the acid of chloroazotic acid burn into oxidized property, but hardly by HCl, H 2sO 4impact.Osmium burn in phosphorous vapor formed phosphide, in sulfur vapor burning formed sulfide.Alkali metal sulphuric acid hydrogen salt, potassium hydroxide and the oxygenant corrosion that osmium is also melted.In short, the fusing point of osmium is about 2700 DEG C, and boiling point is about 5500 DEG C, and density is d 4 2022.61.
The nucleidic mass of iridium (Ir) is 192.217, and ordination number is 77.Naturally occurring isotropic substance is 191 (38.5%), 193 (61.5%), and artificial radioactive isotope is 182-191,194-198.It accounts for about 0.001ppm in the earth's crust.Iridium is that Tennant finds.It is present in nature with metallic state, exists usually used as the native alloy with osmium (osmiridium), finds a small amount of and platina (platinum ore) or forms alloy with native state.Deville is seen, Debray, Ann.Chim.Phys.61,84 (1861) by the recovery of osmiridium and purifying; Wichers is seen, J.Res.Nat.Bur.Stand.10,819 (1933) by the recovery of platinum ore and purifying.Summary about the preparation of iridium and other platinum metals, character and chemistry is shown in: Gilchrist, Chem.Rev.32,277-372 (1943); W.P.Griffith, the Chemistry of the Rare Platinum Metals (John Wiley, NewYork, 1967) 1-41,227-312 page; Livingstone, Comprehensive InorganicChemistry the 3rd volume, J.C.Bailar Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 1163-1189,1254-1274 page.Iridium is silvery white, stone metal, has face-centered cubic lattice, and fusing point is 2450 DEG C, and boiling point is about 4500 DEG C, and density is d 4 2022.65, specific heat is 0.0307cal/g/ DEG C, and Mohs' hardness is 6.5, is that in all elements, proportion is the highest.Pure iridium is not included chloroazotic acid in interior acid corrosion, (non-oxidizing) alkali slight erosion be only melted.It in the oxidation of heating condition lower surface, when red heat by fluorine and chlorine corrosion, is corroded by the mixture of potassium sulfate or potassium hydroxide and saltpetre during melting in atmosphere, is corroded by lead, zinc or tin.Granulated metal is oxidized to dioxide when red heat by air or oxygen, IrO 2, but when heating further, dioxide resolves into its moiety.In short, the fusing point of iridium is 2450 DEG C, and boiling point is about 4500 DEG C, and density is d 4 2022.65.
The nucleidic mass of platinum (Pt) is 195.078, and ordination number is 78, belongs to VIII (10) race.Naturally occurring isotropic substance is 190 (0.01%), 192 (0.8%), 194 (32.9%), 195 (33.8%), 196 (25.2%), 198 (7.2%), and 190 is radioactive: T 1/2be 6.9 × 10 11year.Artificial radioactive isotope be 173-189,191,193,197,199-201.Platinum accounts for about 0.01ppm in the earth's crust.It is believed that Pliny once mentioned it with title " alutiae ", to know for people with " platina delPinto " in South America and use.Platinum is Ulloa report in 1735, takes Europe to and described by Watson in 1741 by Wood.It is present in gravel and sand with the natural form of the alloy with one or more of platinum group member (iridium, osmium, palladium, rhodium and ruthenium).Preparation is shown in Wichers et al, Trans.Amer.Inst.Min, Met.Eng.76,602 (1928).Summary about the preparation of platinum and other platinum metals, character and chemistry is shown in: Gilchrist, Chem.Rev.32,277-372 (1943); Beamish et al., Rare Metals Handbook, C.A.Hampel, Ed. (Reinhold, New York, 1956) 291-328 page; Livingstone, Comprehensive InorganicChemistry, the 3rd volume, J.C.Bailar, Jr.et al., Eds. (Pergamon press, Oxford, 1973) 1163-1189,1330-1370 page; F.R.Harley, The Chemistry of Platinumand Palladium with Particular Reference to Complexes of the Elements (Halsted Press, New York, 1973).Platinum is the metal of silver gray, glossy, extending, flexible, has face-centred cubic structure, with black particle (platinum black) and the preparation of cavernous body (platinum is continuous) form.The fusing point of platinum is 1773.5 ± 1 DEG C; Roeser et al., Nat.Bur.Stand.J.Res.6,1119 (1931)); Boiling point is about 3827 DEG C, and density is d 4 20(21.447 calculated value); Brinell hardness is 55; Specific heat at 0 DEG C is 0.0314cal/g; Resistivity (20 DEG C) is 10.6 μ Ω cm; Be exposed in air and do not tarnish, absorb hydrogen during red heat and at room temperature retain it securely; Gas is discharged during vacuum red heat; Contain carbon monoxide, carbonic acid gas and nitrogen; Obviously volatilize when being heated to 1500 DEG C in atmosphere.The Metal absorption oxygen heated also is discharged when cooling.Platinum does not affect by water or single inorganic acid, reacts and forms Platinic chloride, equally also react with the alkaline cyanide of melting with the chloroazotic acid of boiling.Its by halogen, fused caustic, alkali metrate, alkaline peroxide burn into and in the presence of a reducing agent by arsenate and phosphoric acid salt corrode.In short, the fusing point of platinum is 1773.5 ± 1 DEG C; Roeser et al., Nat.Bur.Stand.J.Res.6,1119 (1931), boiling point is about 3827 DEG C, and density is 21.447 (calculated values).
The nucleidic mass of gold (Au) is 196.96655, and ordination number is 79, belongs to IB (11) race.Naturally occurring isotropic substance is 197; Man-made isotope (total mass number) is 177-179,181,183,185-196,198-203.Gold accounts for 0.005 in the earth's crust.Gold the chances are the first pure metal that the mankind know.It is present in nature with natural form, and minute quantity is present in nearly all rock and seawater.Gold mine comprises calaverite (AuTe 2), sylvanite [(Ag, Au) Te 2], antamokite [(Ag, Au) 2te].Exploitation, to extract and the method for refining is shown in Hull, Stent, Modern ChemicalProcesses, the 5th volume (Reinhold, New York, 1958) 60-71 page.Laboratory preparation from gold plaque to goldc grains is shown in Block, Inorg.Syn 4,15 (1953).The chemistry of the golden medicine for the treatment of rheumatoid arthritis is shown in D.H.Brown, W.E.Smith, Chem.Soc.Rev.9,217 (1980).Passing through NO 2purposes as catalyzer in oxidation of organic compounds is shown in R.E.Sievers, S.A.Nyarady, J.Am.Chem.Soc.107,3726 (1985).The metal reactive minimum in the interface with gas or liquid is shown in B.Hammer, J.K.Norskov, Nature 373,238 (1995).Summary: Gmelin ' s Handb.Anorg.Chem., Gold (the 8th edition) the 62,2nd, 3 parts (1954); Johnson, Davis, " Gold ", Comprehensive InorganicChemistry, the 3rd volume, J.C.Bailar Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 129-186 page; J.G.Cohn, E.W.Stern, Kirk-Othmer Encyclopedia ofChemical Technology the 11st volume (Wiley Interscience, New York, the 3rd edition, 1980) 972-995 page.Gold is yellow soft metal, has face-centred cubic structure, obtains intense violet color, purple or Ruby red particle when being prepared by volatilization or the precipitator method, fusing point is 1064.76 DEG C, and boiling point is 2700 DEG C, and density is 19.3, Mohs' hardness is 2.5-3.0, and Brinell hardness is 18.5.Gold is torpescence extremely; Acid and alkali, air or oxygen corrode; By halogen aqueous corrosion surface under room temperature; React with chloroazotic acid, if the mixture containing muriate, bromide or iodide can produce newborn halogen, with this mixture reaction, with the solution reaction of many oxidizing mixtures especially containing halogen, alkaline cyanide, thiocyanate-and double cyanide.In short, the fusing point of gold is 1064.76 DEG C, and boiling point is 2700 DEG C, and density is 19.3.
The nucleidic mass of rhenium (Re) is 186.207, and ordination number is 75, belongs to VIIB (7) race.Naturally occurring isotropic substance is 185 (37.07%), 187 (62.93%), and the latter is radioactive, T 1/2be about 10 11year; Artificial radioactive isotope be 177-184,186,188-192.Rhenium accounts for about 0.001ppm in the earth's crust.It is present in ytterbite, molybdenum glance, niobite, rare-earth mineral and some sulfide ores.Rhenium is that Nodack etc. finds (Naturwiss.13,567,571 (1925)).Rhenium metal is shown in Hurd, Brim, Inorg.Syn1,175 (1939) by the preparation of the reduction of potassium perrhenate or ammonium perrhenate, and the preparation of high purity rhenium is shown in Rosenbaum et al., J.Electrochem.Soc.103,18 (1956).Summary: Mealaven, Rare Metals Handbook, C.A.Hampel, Ed. (Reinhold, New York, 1954) 347-364 page; Peacock, ComprehensiveInorganic Chemistry the 3rd volume, J.C.Bailar, Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 905-978 page; P.M.Treichei, Kirk-Othmer Encyclopediaof Chemical Technology the 20th volume (Wiley-Interscience, New York, the 3rd edition, 1982) 249-258 page.Rhenium has Hexagonal close and piles up crystallization, and for black to silver gray, density is d 21.02, fusing point is 3180 DEG C, boiling point is 5900 DEG C (estimations), and specific heat (0-20 DEG C) is 0.03263cal/g/ DEG C, and ratio resistance (20 DEG C) is 0.21 × 10 -4Ω/cm, Brinell hardness is 250, vaporization heat is 152kcal/mol, does not react with oxidizing acid, nitric acid and strong sulfuric acid response with HCl.In short, the fusing point of rhenium is 3180 DEG C, and boiling point is 5900 DEG C (estimations), and density is 21.02.
The ordination number of neptunium (Np) is 93.It is that the first does not have the artificial transuranium element of stable nuclide.Known isotropic substance (total mass number) is 227-242.Isotropic substance 239 (T 1/22.355 days, alpha decay, relative atomic mass 239.0529) discovery visible E.McMillan, P.Abelson, Phys.Rev.57,1185 (1940); Isotropic substance 237 (T 1/22.14 × 10 6year, the known isotropic substance of longest-lived, relative atomic mass 237.0482) discovery visible A.C.Wahl, G.T.Seaborg, ibid.73,940 (1948).S.Fried is shown in the preparation of metal, N.Davidson, J. Am.Chem.Soc.70,3539 (1948); L.B.Magnusson, T.J.LaChapelle, ibid.3534.Neptunium is shown in Seaborg in the existence of occurring in nature, Perlman, ibid.70,1571 (1948).Chemical property is shown in Seaborg, Wahl, ibid.1128.Summary: C.Keller, the chemistry of theTransactinide Elements (Verlag Chemie, Weinheim, English Ed., 1971) 253-332 page; W.W.Schulz, G.E.Benedict, Neptunium-237:Production andRecovery, AEC Critical Review Series (USAEC, Washington D.C.), 1972) the 85th page; Comprehensive Inorganic Chemistry the 5th volume, J.C.Bailar, Jr.etal., Eds. (Pergamon Press, Oxford, 1973) passim; J.A.Fahey, TheChemistry of the Actinide Elements the 1st volume, J.J.Katz et al., Eds (Chapman and Hall, New York, 1986) 443-498 page; G.T.Seaborg, Kirk-Othmer Encyclopedia of Chemical Technology the 1st volume (Wiley-Interscience, New York, the 4th edition, 1991) 412-444 page.Neptunium is argentine, forms thin oxide layer when the short period of time is exposed in air.NpO is formed with air reaction under high temperature 2, there is the extrapolation boiling point of 4174 DEG C.Neptunium obtains five oxidation state in the solution; The most stable is pentavalent state.Tetravalent neptunium is easy to be oxidized to hexavalent state by cold permanganate or strong oxidizer; In nitrogen atmosphere, electrolytic reduction obtains trivalent form.In short, the fusing point of neptunium is 637 DEG C, and boiling point is 4174 DEG C, and density is d 20.45; D 19.36.
The ordination number of plutonium (Pu) is 94, does not have stable nucleic.Known isotropic substance (total mass number) is 232-246.The known isotropic substance of MaLS is 242pu (T 1/23.76 × 10 5year, relative atomic mass 242.0587), 244 (T 1/28.26 × 10 7year, relative atomic mass 244.0642).Commercial useful isotropic substance is 238pu (T 1/287.74, relative atomic mass 238.0496), 239pu (T 1/22.41 × 10 4year, relative atomic mass 239.0522).Plutonium accounts for 10 in the earth's crust -22%.Isotropic substance 238the discovery of Pu is shown in G.T.Seaborg et al., Phys.Rev.69,366,367 (1946); Isotropic substance 239j.W.Kennedy et al. is shown in the discovery of Pu, ibid 70 555 (1946).From uraninite 239the solution of Pu is shown in G.T.Saborg, M.L.perlman, J.Am.Chem.Soc.70,1571 (1948).B.B.Cunningham is shown in the preparation of metal, L.B.Werner, ibid.71,1521 (1949).Chemical property is shown in Seaborg, Wal, ibid.1128; Harvey et al., J.Chem.Soc.1947,1010.Summary: J.M.Cleveland, the Chemistry of Plutonium (Gordon & Breach, New York, 1970) the 653rd page; C.Keller, The Chemistryof the Transuranium Elements (Verlag Chemie, Weinheim, English Ed., 1971) 333-484 page; Comprehensive Inorganic Chemistry the 5th volume, J.C.Bailar, Jr.et al., Eds. (Pergamon Press, Oxford, 1973) passim; Handb.Exp.Pharmakol 36 307-688 (1973); F.Weigel, Kirk-Othmer Encyclopediaof Chemical Technology the 18th volume (Wiley-Interscience, New York, the 3rd edition, 1982) 278-301 page; Plutonium Chemistry, W.T.Carnall, G.R.Choppin, Eds. (Am.Chem.Soc., Washington, D.C., 1983) the 484th page; F.Weigel etc., The Chemistry of the Actinide Elements the 1st volume, J.J.Katz et al., Eds. (Chapman and Hall, New York, 1986) 499-886 page.Toxicology summary is shown in W.J.Bair, R.C.Thompson, Science 183,715-722 (1974); Healthy effect is shown in Toxicological Profile for Plutonium (PB91-180406,1999) the 206th page.Plutonium is silvery white metal, has highly reactive.It is easy to oxidation in dry air and oxygen, and speed is accelerated in the presence of moisture.In short, the fusing point of plutonium is 640 ± 2 DEG C, and density is d 2119.86; d 19017.70; d 23517.14; d 32015.92; d 40516.00; d 49016.51.
The nucleidic mass of tantalum (Ta) is 180.9479, and ordination number is 73, belongs to VB (5) race.Naturally occurring isotropic substance is 181 (99.9877%); 180 (0.0123%), T 1/2> 10 12year; Artificial radioactive isotope is 172-179; 182-186.Tantalum almost always with niobium association, but content do not have niobium enrich.Tantalum is present in niobite, tantalite ([(Fe, Mn) (Ta, Nb) 2o 6]) and microlite [(Na, Ca) 2ta 2o 6(O, OH, F)] in.Tantalum was found in 1802 by Edeberg; First its pure substance obtains (Z.Elektrochem.11,45 (1905)) by Bolton.Preparation is shown in Schoeller, Powell, J.Chem.Soc.119,1927 (1921).Summary: G.L.Miller, Tantalum andNiobium (Academic Press, New York, 1959) the 767th page; Brown, " TheChemistry of Niobium and Tantalum ", Comprehensive InorganicChemistry the 3rd volume, J.C.Bailar, Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 553-622 page.Tantalum is the metal of grey, stone, extending, toughness, and it can be easy to pull into filament; Fusing point is 2996 DEG C, boiling point is 5429 DEG C, density is d 16.69, specific heat (0 DEG C) is 0.036cal/g/ DEG C, resistivity (18 DEG C): 12.4 μ Ω cm, water insoluble, very resistance to chemical attack, not by other acid corrosion outside hydrofluoric acid, also do not corroded by alkali aqueous solution, the alkali be melted slowly corrodes.It only reacts with fluorine, chlorine and oxygen under heating, and at high temperature absorbs hundred times in the hydrogen of own vol; Close with nitrogen, carbonization.In short, the fusing point of tantalum is 2996 DEG C, and boiling point is 5429 DEG C, and density d is 16.69.
In a lot of polymer materials matrix material used in the present invention.With regard to the object of the application, polymkeric substance this general terms cover heating solidity and thermoplastic material.We have found that polymer materials used in the present invention comprises polycondensation material and addition or vinyl polymerization material.Included is vinyl polymer and polycondensate and polymer alloy thereof.Vinyl polymer is manufactured by the monomer polymerization with the unsaturated ethylenic group of ethylenic usually.Polycondensate utilizes the polycondensation preparation being commonly referred to be progressively chemical reaction usually, wherein makes two or more molecule chemical combination, often but must with the separation of water or some other simple normally volatile materials.This polymkeric substance can be formed in the process being called polycondensation.The density of described polymkeric substance is at least 0.85g/cm 3, but the polymkeric substance that density is greater than 0.96 is useful for the global density improving product.Depend on metallic particles and end-use, density Chang Zhigao is 1.7 or paramount for 2g/cm 3or can be about 1.5-1.95g/cm 3.
Vinyl polymer comprises polyethylene, polypropylene, polybutene, acrylonitrile-butadiene-styrene (ABS) (ABS), polybutene copolymer, poly-acetyl resin, polyacrylics, comprises vinylchlorid, the homopolymer of vinylidene chloride or multipolymer, fluorocarbon copolymer etc.Polycondensate comprises nylon, phenoxy resin, polyarylether as polyphenylene oxide, polyphenyl thioether material; Polycarbonate material, oxetane resin, polyethersulfone resin, polyphenylene oxide resin, polysulfone resin, polyimide resin, Polyurethane Thermoplastic Elastomer and other resin materials many.
Polycondensate in matrix material used in the present invention comprises polymeric amide, polyamide-imide polymer, polyarylsulphone, polycarbonate, polybutylene terephthalate, PBN, polyetherimide, polyethersulfone, polyethylene terephthalate, thermoplastic polyimide, polyphenylene ether blend, polyphenylene sulfide, polysulfones, thermoplastic polyurethane etc.Preferred condensation engineering polymers comprises polycarbonate material, polyphenyl ether material and polyester material (comprising polyethylene terephthalate, polybutylene terephthalate, PEN and PBN material).
Polycarbonate engineering polymers is high-performance, unbodied engineered thermoplastic materials, and it has high impact, transparency, thermotolerance and dimensional stability.Polycarbonate is usually divided into polyester or has the carbonic acid of organic hydroxy compounds.The most frequently used polycarbonate is based on as the phenol A of oxy-compound and carbonic acid copolymerization.Material is usually by dihydroxyphenyl propane and phosgene (O=CCl 2) reaction preparation.Polycarbonate by polymerization forcing machine in introduce phthalate ester monomers preparation with improving SNR as thermotolerance, trifunctional material also can be used in addition to increase melt strength or extrusion-blown modling material.In alloying, polycarbonate often can be used as the component combined with other commercial polymer and uses as general intermingling material.Polycarbonate can with the combinations such as polyethylene terephthalate, acrylonitrile-butadiene-styrene (ABS), styrene-maleic anhydride.Preferred alloy comprises styrol copolymer and polycarbonate.The melt index of preferred polycarbonate material should be 0.5-7g/10 minute, preferred 1-5g/10 minute.
In multiple polycondensation of polyester thing material matrix material used in the present invention, comprise polyethylene terephthalate, polybutylene terephthalate, PEN, PBN etc.Polyethylene terephthalate and polybutylene terephthalate are high performance polycondensate material.This base polymer is prepared usually through the copolymerization between glycol (ethylene glycol, BDO) and dimethyl terephthalate (DMT).In the polymerization of this material, polyblend is heated to high temperature and the transesterification reaction of methyl alcohol occurs to discharge and forms engineering plastics.Equally, PEN and PBN material can be prepared by the same copolymerization as acid source with naphthalic acid.Compared with terephthalic acid ester material, naphthalate thermoplastic material has the high-temperature stability of higher Tg and Geng Gao.But in all these polyester materials matrix material all used in the present invention.It is the preferred molecular weight of feature that this kind of material has with fluidity of molten.The viscosity of useful polyester material at 265 DEG C is about 500-2000cP, preferably about 800-1300cP.
Polyphenyl ether material is engineered thermoplastic materials, can be used in the temperature range up to 330 DEG C.Polyphenylene oxide has excellent mechanical property, dimensional stability and dielectric characteristics.Usually, polyphenylene oxide is produced as the polymer alloy or blend with other polymkeric substance or fiber and is sold.Polyphenylene oxide comprises the homopolymer of 2,6-dimethyl-1-phenol usually.Described polymkeric substance is often called as poly-(oxygen-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene)).The alloy of polyphenylene oxide Chang Yiyu polymeric amide (normally nylon 6-6) or blend, to use with the alloy of polystyrene or HI high impact vinylbenzene etc.The preferred melt index of polyphenyl ether material (ASTM 1238) that can be used in the present invention is generally about 1-20g/10 minute, preferably about 5-10g/10 minute.Melt viscosity at 265 DEG C is about 1000cP.
Another kind of thermoplastic material comprises styrol copolymer.Term styrol copolymer refers to that vinylbenzene and the second vinyl monomer copolymerization obtain vinyl polymer.This kind of material contains the vinylbenzene of at least 5 % by mole, and all the other are other vinyl monomers one or more of.An important kind in these materials is styrene-acrylonitrile (SAN) polymkeric substance.SAN polymkeric substance is random amorphous linear copolymers, is produced by vinylbenzene, vinyl cyanide and other optional monomer copolymerization.Emulsion, suspension and continuous bulk polymerization technology are used.San copolymer has the transparency, excellent thermal characteristics, good chemical resistant properties and hardness.These polymkeric substance also with its rigidity, dimensional stability and supporting capacity for feature.Olefin-modified SAN (OSA polymer materials) and acrylic acid or the like (acrylic) styrene-acrylonitrile (ASA polymer materials) are known.These materials are slightly softer than unmodified SAN, are flexible, opaque two-phase terpolymer, have the weathering resistance of beat all improvement.
ASA polymkeric substance is random amorphous terpolymer, produces by bulk copolymerization or by graft copolymerization.In bulk copolymerization, acrylic monomer, vinylbenzene and vinyl cyanide are combined to form mixed embedding terpolymer.In another kind of technology of preparing, styrene-acrylonitrile oligopolymer and monomer can be grafted on acrylic elastomer main chain.This kind of material has the feature being used as outdoor weather-proof and the product of resistance to UV, and described product has excellent colour stability confining force and stable in properties when outdoor exposure.These materials also can with other polymkeric substance multiple (comprising polyvinyl chloride, polycarbonate, polymethylmethacrylate etc.) blended or alloying.The important styrol copolymer of one class comprises acrylonitrile-butadiene-styrene (ABS) monomer.These polymkeric substance are engineered thermoplastic materials of non-normal open, are produced by described three kinds of monomer copolymerizations.Each monomer provides important character for final terpolymer material.Final material has excellent thermotolerance, chemical resistant properties and surface hardness and workability, rigidity and intensity.Described polymkeric substance is also tough and tensile and impact-resistant.The melt index of styrol copolymer base polymer is about 0.5 to 25, preferably about 0.5 to 20.
The important engineering polymers of a class in matrix material used in the present invention comprises acrylic polymers.Acrylic polymers comprises polymkeric substance and multipolymer widely, and wherein main monomer component is acrylate or methacrylic ester.These polymkeric substance often provide with hard clear sheet or pellet form.The free radical proceed that acrylic monomer is caused by superoxide, azo-compound or radiating capacity is usually polymerized.Often provide commercial polymer to fill a prescription, wherein various additive is properties-correcting agent used between polymerization period, for application-specific provides a series of specified property.For the pellet of grade polymer application preparation is usually or with mass polymerization (continuous solution polymerization), then extrude and granulation and preparing; or be polymerized in an extruder continuously and prepare, unconverted monomer decompression is shifted out and circulation and stress in an extruder.Acrylics usually with methyl acrylate, methyl methacrylate, vinylformic acid higher alkyl esters and other can copolymerization vinyl monomer preparation.The melt index of the preferred acrylic polymeric material in matrix material used in the present invention is about 0.5-50g/10 minute, preferably about 1-30g/10 minute.
Vinyl polymer comprises vinyl cyanide; Alpha-olefin is as the polymkeric substance of ethene, propylene etc.; Chlorinated monomer is if vinylchlorid, vinylidene chloride, acrylate monomer are as vinylformic acid, methyl acrylate, methyl methacrylate, acrylamide, Hydroxyethyl acrylate etc.; Styrene monomer is as vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.; Vinyl acetate; Usually the ethylenically unsaturated monomers composition that obtains is easy to other.
Blend polymer or polymer alloy can be used in the production of pellet of the present invention or linear extrudate.This kind of alloy comprises two kinds of polymkeric substance that can mix usually, its blended formation homogeneous compositions.Science in blend polymer field and commercial advance have caused realizing not reached important physicals by development of new polymer materials improve by forming the blend polymer that can mix or alloy.The polymer alloy of equilibrium state comprises the mixture of two kinds of amorphous polymers, and described two kinds of polymkeric substance exist as the single-phase of the tight mixing segment of two kinds of macromolecular components.Namely the amorphous polymer that can mix forms glass once enough coolings, and the blend polymer that evenly maybe can mix has the single second-order transition temperature (Tg) depending on composition.Can not to mix or the blend polymer of no-alloyed usually shows two or more second-order transition temperatures with the polymer phase that can not mix.In the simplest situations, the composition weighted mean reflection of the performance that had by each component of the performance of polymer alloy.But generally speaking, performance to the dependency of composition in a complex manner with the characteristic (glassy, rubber-like or hypocrystalline) of specific performance, component, the thermodynamic state of blend and molecule thereof and mutually whether orientation machine performance and change.
Keep enough thermoplasticity for the basic basic demand for engineering thermoplastic's polymer materials, as viscosity and stability, with allow melt and metallic particles is blended, allow to form linear extrudate pellet and allow composition material or pellet to extrude in thermoplastic process or injection molding with the product be formed.Engineering polymers and polymer alloy can be buied from many manufacturer, comprise Dyneon LLC, B.F.Goodrich, G.E., Dow and duPont.
Polyester polymers is produced by the reaction of diprotic acid and dibasic alcohol.Tetra hydro Phthalic anhydride, m-phthalic acid, toxilic acid and hexanodioic acid is comprised for the diprotic acid in production of polyester.Phthalic acid provides rigidity, hardness and temperature tolerance; Toxilic acid provides vinyl saturated to adapt to radically curing; Hexanodioic acid provides flexible and toughness for cure polymer.Conventional dibasic alcohol is propylene glycol, and it reduces crystallization and is inclined to and improves the solvability in vinylbenzene.Ethylene glycol and glycol ether reduce crystallization tendency.Diprotic acid and dibasic alcohol eliminate water through condensation, are then dissolved in vinyl monomer to suitable viscosity.Vinyl monomer comprises vinylbenzene, Vinyl toluene, p-methylstyrene, methyl methacrylate and Phthalic acid, diallyl ester.Add polymerization starter if quinhydrones, tert-butyl catechol or phenothiazine are to extend the preservation period of uncured polyester polymers.Polymkeric substance based on Tetra hydro Phthalic anhydride is called as phthalic acid polyester, and the polymkeric substance based on m-phthalic acid is called as isophthalic polyester.The viscosity of unsaturated polyester ester polymer can be regulated according to application.Low viscosity in the manufacture of fibre reinforced composites for guaranteeing that good wettability and the enhancement layer follow-up height to base material below adheres to very important.Wettability difference can cause the significantly loss of mechanical property.Usually, polyester production uncured viscosity is concentration of styrene or the production of other monomer concentration of the polymkeric substance of 200-1,000MPa.s (cP).The viscosity of tailor-made polymer thing can be about 20cP to 2,000cP.The radical initiator that unsaturated polyester ester polymer is produced by conventional peroxide material usually solidifies.Multiple peroxide initiator all has commercially available and conventional.Peroxide initiator thermolysis forms free radical initiation kind.
Phenol polymer also can be used for manufacturing structure unit of the present invention.Phenol polymer comprises phenol-aldehyde polymer usually.This base polymer person's character is fire-resistant, heat-resisting and cost is low.Phenol polymer is prepared by blended phenol and the formaldehyde lower than stoichiometry usually.These material use acid catalyst condensations produce the thermoplasticity midbody polymer being called NOVOLAK.These polymkeric substance are the oligopolymer of phenolic group end-blocking.In the presence of a curing agent with under optionally heating, described oligopolymer solidify to form the very high thermosetting polymer of molecular weight.Solidifying agent for novalak is generally aldehyde cpd or methylene radical (-CH 2-) to body.Aldehydes solidifying agent comprises paraformaldehyde, vulkacit H, formaldehyde, propionic aldehyde, oxalic dialdehyde and hexamethyl methoxyl group melamine.
The fluoropolymer that can be used in the present invention is the multipolymer of perfluorination and partially fluorinated polymkeric substance or two or more this kind of monomers obtained by the monomer containing one or more fluorine atom.The common instance that can be used for the fluorinated monomer in these polymkeric substance or multipolymer comprises tetrafluoroethylene (TFE), R 1216 (HFP), vinylidene fluoride (VDF), perfluoroalkyl vinyl ether as perfluor-(n-propyl-vinyl) ether (PPVE) or perfluoro methyl vinyl ether (PMVE).Other can the olefin monomer (comprising non-fluorinated monomer) of copolymerization also can exist.
For fluoropolymer, useful especially material is that (melt temperature is about 100 to 260 DEG C to TFE-HFP-VDF terpolymer; Melt flow index under 265 DEG C and 5kg load is about 1-30g/10 minute), (melt temperature is about 150 to 280 DEG C to R 1216-tetrafluoroethylene-Ethylene (HTE) terpolymer; Melt flow index under 297 DEG C and 5kg load is about 1-30g/10 minute), (melt temperature is about 250 to 275 DEG C to ethylene-tetrafluoroethylene (ETFE) multipolymer; Melt flow index under 297 DEG C and 5kg load is about 1-30g/10 minute), (melt temperature is about 250 to 275 DEG C to R 1216-tetrafluoroethylene (FEP) multipolymer; Melt flow index under 372 DEG C and 5kg load is about 1-30g/10 minute) and tetrafluoroethylene-perfluoro (alkoxy alkane) (PFA) multipolymer (melt temperature is about 300 to 320 DEG C; 372 DEG C is about 1-30g/10 minute with the melt flow index under 5kg load).Each in these fluoropolymers all can from Dyneon LLC, and Oakdale, Minn buy.TFE-HFP-VDF terpolymer is sold with title " THV ".
Also the vinylidene fluoride polymer made primarily of interpolymerized vinylidene fluoride monomer be can use, homopolymer and multipolymer comprised.This analog copolymer comprises containing those of the vinylidene fluoride of at least 50 % by mole and at least one monomer copolymerization, and described monomer is selected from tetrafluoroethylene, trifluoro-ethylene, chloro trifluoro ethylene, R 1216, vinyl fluoride, five fluorine propylene and is easy to other monomer any with vinylidene fluoride copolymerization.These materials are also described in United States Patent (USP) 4, and in 569,978 (Barber), this patent is incorporated to herein by reference.Preferred multipolymer is (as English Patent 827 by the multipolymer made to the vinylidene fluoride of 99 % by mole and the tetrafluoroethylene of corresponding about 1 to 30% at the most at least about 70, disclosed in 308) and the multipolymer be made up of the vinylidene fluoride of about 70 to 99% and the R 1216 of 1 to 30% (see such as United States Patent (USP) 3,178,399) multipolymer and by the vinylidene fluoride of about 70-99 % by mole and the trifluoro-ethylene of 1-30% made.The terpolymer of vinylidene fluoride, trifluoro-ethylene and tetrafluoroethylene is (as United States Patent (USP) 2,968, described in 649) and the terpolymer of vinylidene fluoride, trifluoro-ethylene and tetrafluoroethylene be also the representative example of the vinylidene fluoride copolymer class that can be used in the present invention.This kind of material can trade(brand)name KYNAR from be positioned at Pennsylvania's Jin Gefupu western Shandong Asia Arkema Group or with trade(brand)name DYNEON from Dyneon LLC of Oakdale, MN buys.Fluorocarbon elastomer material is also in matrix material used in the present invention.Fluoropolymer is containing VF 2with HFP monomer and optionally containing TFE, and density is greater than 1.8g/cm 3.Fluoropolymer has good patience to most of oil, chemical, solvent and halohydrocarbon, and has excellent patience to ozone, oxygen and weather.Its available temperature limit is-40 DEG C to 300 DEG C.The example of fluoroelastomer comprises the United States Patent (USP) 4,257 of Lentz, describe in the United States Patent (USP) 5,061,965 of the United States Patent (USP) 5,017,432 of those and the Eddy that describe in detail in 699 etc. and Ferguson etc. those.The disclosure of each in these patents is all incorporated to herein by reference.
Latex fluoropolymer can obtain with the form comprising the polymkeric substance of PFA, FEP, ETFE, HTE, THV and PVDF monomer.Fluoridizing poly-(methyl) acrylate can use radical initiator well known to those skilled in the art by body or solvent radical polymerization preparation usually.Other monomer can fluoridizing the copolymerization of (methyl) acrylate monomer with these comprises (methyl) alkyl acrylate, (methyl) alkyl acrylate of replacement, (methyl) vinylformic acid, (methyl) acrylic amide, styrenic, halogen vinyl and vinyl ester.Fluoropolymer can comprise polar component.The monomer of this kind of polar group or polar functionalities can be negatively charged ion, nonionic, positively charged ion or both sexes.Usually, comparatively conventional polar group or the organic group of polar functionalities comprise organic acid, particularly carboxylic acid, sulfonic acid and phosphonic acids; Carboxylate salt, sulfonate, phosphonate, phosphoric acid ester, ammonium salt, amine, acid amides, alkylamide, alkylaryl amides, imide, sulphonamide, methylol, mercaptan, ester, silane and polyoxyalkylene, and other organic group as the alkylidene group that replaces by one or more this kind of polar group or arylidene.Latex fluoropolymer normally water dispersible solid described herein, but can solvent material be used.Fluoropolymer can be combined to form the dispersion of emulsion, solution or liquid form with all kinds of SOLVENTS.The dispersion of fluoropolymer can be standby by conventional emulsion polymerization legal system, such as United States Patent (USP) 4,418,186,5,214,106,5,639,838,5,696,216 or John scheirs while the Modern Fluoropolymers (particularly 71-101 and 597-614 page) and the transferee that submits to January 31 calendar year 2001 of editor in 1997 described in unexamined patent application sequence number 01/03195.
Liquid form also can through diluting to reach required concentration further.Although water miscible liquid, solution and dispersion are preferred, the solubility promoter of many about 50% can be added to as methyl alcohol, Virahol or methyl perfluorobutyl ether.Preferably, water miscible liquid, solution and dispersion comprise the solubility promoter lower than about 30%, more preferably less than the solubility promoter of about 10%, and the most preferably basic co-solvent of water miscible liquid, solution and dispersion.
The interface modifier used in the application contains classification widely, comprises such as stearic aeic derivative, silane compound, titanate compound, zirconate compound, Aluminate compound.The selection of interface modifier is determined by metallic particles, polymkeric substance and application.The maximum density of matrix material is the function of density of material and each material volume fraction.The matrix material of higher density obtains by making per unit volume have the maximization of the most highdensity material.Described material is only almost that refractory metal is as tungsten or osmium.These materials are hard especially and be difficult to distortion, often cause brittle rupture.When with deformable polymer binder mixture, these hard brittle materials can be formed as useful shape with traditional thermoplasticity device.But obtainable maximum density will lower than optimum value.When forming polymer volume and approximating the matrix material of the excluded volume of filler, intergranular interaction is by the behavior of domination material.Particle contacts with each other, and the friction between the combination on interactional sharpened edge, soft surface (cause cutter hole, put normal work hardening) and surface stops best accumulation further.Therefore, maximized performance is the function of pressure, circularity and common shape on Surface softness, edge hardness, the some size (acutance) of point, skin friction force and material, distribution of sizes.Due to this intergranular friction, compacting pressure exponentially reduces with exerted a force distance.Interface modification chemical energy is by the surface of the combination modified densification weighting agent of coordinate bond, Van der Waals force, covalent linkage or this threes all.The surface exhibits of particle is the particle of the non-reactive end of interface modifier.These organism reduce intergranular friction, thus prevent cutter from cheating and allowing freedom of motion larger between particle.These phenomenons make applied plastic force deeper can arrive inside configuration and cause evenly pressure gradient.
Stearic acid compound modification matrix material of the present invention, in surface of metal particles, the formation of stearic acid layer reduces intermolecular forces, improves tendency that polymkeric substance mixes with metallic particles and composite density is increased.Similarly, silane interface modifier is by metallic particles formation chemical bond alternate with continuous polymer or make it to match with the surface energy polymer of particulate polymers interface by the surface energy changing inorganic metal particle and improve the physicals of matrix material.The silane coupling agent that can be used in the present invention includes but not limited to the compound of following structure:
R-(CH 2) n-Si-X 3
Wherein X represents hydrolyzable group, comprises alkoxyl group, acyloxy, halogen or amine, depends on surface chemistry and the reaction mechanism of metallic particles.Coupling maximizes with the maximization of chemical bond quantity between particle surface and polymkeric substance.When matrix material by be used to comprise a large amount of aqueous medium and wide range of temperature application in time, select both arms silane (dipodal silane) as two (triethoxysilyl) ethane.These materials have following structure:
R[(CH 2) n-Si-X 3] 2
Wherein R represents the non-hydrolysable organic group of silane compound.If R group can chemical bonding to the interface modification words applicatory of polymer phase or nonbonding; keep unreacted as desired.When R chemical bonding is to polymer phase, these free radicals add by heat, light or the form with peroxide catalyst or promotor and similar reaction system.In addition the selection of R group need consider the polymkeric substance that uses in matrix material.If selection thermosetting polymer, then can carry out chemical bonding silane to polymer phase with thermosetting polymer.Active group in thermosetting material can comprise methacryloyl, styryl or other unsaturated or organic materials.
Thermoplastic material comprise polyvinyl chloride, polyphenylene sulfide (polyphenylene sulfite), acrylic homopolymer, polymkeric substance containing maleic anhydride, acrylic material, vinyl acetate polymer, containing the multipolymer of diene (as 1; 3-divinyl, Isosorbide-5-Nitrae-pentadiene), the polymkeric substance of halogen or chlorosulfonyl modification or other polymkeric substance that can react with composite system of the present invention.By end group with have aminoalkyl group, chlorine alkyl, isocyanato or similar functional group silane reaction use polycondensation thermoplastic material, comprise polymeric amide, polyester, polycarbonate, polysulfones and similar polymer materials.
Good production technology is depended in the production of high desnity metal particulate composite.Usual metallic particles first through interface modifier as reactive silane process, way be with 25 % by weight silane or the solution spraying of other interface modifier on metallic particles and blended and careful drying to guarantee the even coatedparticles of interface modifier.Interface modifier such as silane also can utilize high strength Littleford or Henschel blending machine to be added in particle in batch blended (bulk blending) operation.As selection, duoble cone-type blender can be sent into before the drying, or directly be added in screw rod mixing device.Interface modifier also can react with metallic particles in aprotic solvent is as toluene, tetrahydrofuran (THF), petroleum solvent or other this kind of known solvent.
Metallic particles can with polymer phase coupling, depend on any pigment processing aid of existing or additive in the character of polymer phase, filler, particle surface chemistry and matrix material.In general, being used for the mechanism of coupling metallic particles and polymkeric substance comprises solvation, chelating, coordination bonding (part is formed) etc.Titanic acid ester or zirconium ester coupling agent can be used.This kind of coupling agent has following formula:
(RO) m-Ti-(O-X-R’-Y) n
(RO) m-Zr-(O-X-R’-Y) n
Wherein m and n is 1 to 3.Titanic acid ester provides oxidation-resistance and can change or control curing chemistry.Zirconate provides excellent bond strength and solidification is maximized, and is reduced in the thermoplastic material of preparation and forms color.Useful zirconate materials is neo-pentyl (diallyl) oxygen-three (dioctyl) phosphate-based zirconate.
The high desnity metal polymer composites with required physical properties can by following production.In preferred mode, first prepare surface of metal particles, interface modifier reacted with obtained particulate material, separating obtained product, then and continuous print polymer phase combine with realization response between metallic particles and polymkeric substance.Once prepare matrix material, then it be formed the shape needed for end-use material.Another program is in material processing, provide the solution of solvent recuperation to process.Material also can solvent-freely be dry mixed.The ribbon formula mixing machine of blended system Tathagata from Drais Systems, the high-density driving mixing machine from Littleford Brothers and Henschel acquisition can be used.Also other melt blending using Banberry, veferralle singe screw or twin screw compounder can be adopted.When material adds man-hour as the plastisol or organosol with solvent, liquid component is first added in processing unit (plant) usually, then adds polymkeric substance, metallic particles rapid stirring.Once add all material, can apply vacuum with remove remaining air and solvent and continue mixing until product evenly and obtain high-density.
Due to cost advantage, be usually preferably dry mixed.But some embodiment may be unstable on composition due to the difference of particle diameter.In dry mixing process, matrix material is prepared: first introduce polymkeric substance by following steps, if need to merge polymer stabilizer and described polymkeric substance in about room temperature at the temperature of about 60 DEG C, blended metallic particles (if needing through modification) is with described through stable polymkeric substance, other processing aid of blending, interface modifier, tinting material, indicator or lubricant, then mix in hot mixing tank, be transferred to storage, packaging or end-use and produce.
The material useable solvents technology preparation of interface modification, described solvent technology uses the solvent of significant quantity to cause the formation of matrix material.When interface modification completes substantially, solvent can be gone out by stripping.This kind of solvent method is performed as follows:
1) interface modifier or polymkeric substance or the two solvation is made;
2) metallic particles is mixed in body phase or polymer master batch; With
3) under the existence of heat and vacuum, slough the volatile component in composition at higher than the temperature of polymer Tg.
When by twin screw compounder or forcing machine mixture, the selection process relating to twin screw mixture as follows can be used.
1. add metallic particles and removing surface water (machine barrel 1) that heats up.
2. in twin screw, add interface modifier (machine barrel 3) when filler is in suitable temperature.
3. dispersion/distribution interface modifier on metallic particles.
4. maintain temperature of reaction to having reacted.
5. discharge byproduct of reaction (machine barrel 6).
6. add polymer binder (machine barrel 7).
7. compression/molten polymer adhesive.
8. dispersion/distribution polymer binder in particle.
9. make modified particles and polymer binder react.
10. pair remaining reaction product vacuum outgas (machine barrel 9).
11. compression gained matrix materials.
12. form desired shape, pellet, wire rod, pipe, injection-molded item etc. by step after die head or production.
As selection, in the formula containing small volume external phase:
1. add polymer binder.
2. in twin screw, add interface modifier when polymer binder is in suitable temperature.
3. dispersion/distribution interface modifier in polymer binder.
4. add filler and dispersion/distribution particle.
5. be warming up to temperature of reaction.
6. maintain temperature of reaction to having reacted.
7. compress gained matrix material.
8. form desired shape, pellet, wire rod, pipe, injection-molded item etc. by step after die head or production.
The specific selection of polymkeric substance and particle can allow to save interface modifier and relevant procedure of processing thereof.
Metal polymer composite of the present invention can be used for multiple embodiments, comprises projectile, bait, fishing pendant, automobile counterbalance, radiation shielding, golf ball pole member, sports equipment, gyro ballast (gyroscopic ballast), mobile phone vibrations counterbalance weight or laboratory and intercepts the weight of noise and vibrations or other needs to have plasticity-, toughness and dimensional stability, thermal conductivity, electroconductibility, magnetic and in the embodiment of nontoxic high density material.
The high density material of the present invention and all embodiments thereof is all applicable to multiple working method.The selection of working method and base mateiral formula can based on the needs of required end-use product.The following examples will be illustrated this point.
One embodiment of the invention are for can be used for flexibility in projectile (comprise musket bullet and other ammunition), heart or artery support or radiation shielding clothes or malleable matrix material.The exemplary composite material with these features can comprise tungsten, as the fluoropolymer of tackiness agent and the combination of zirconate interface modifier.End-use product can be to be extruded or the product of moulding.
Another embodiment of the present invention is the high yield, the high density composite that can be used for bait or fish in pendant or mobile phone shielding or internal vibration mechanism.The exemplary composite material with these features can comprise tungsten, as the polyvinyl chloride of tackiness agent and the combination of alkali metal stearic acid salt or stearylamide interface modifier.End-use product can be to be extruded or the product of moulding.
Another embodiment of the present invention be can be used for automobile or truck inflation tire wheel counterbalance weight or other ballast or other can low yield in the product produced of block form, long set time and high density composite.The exemplary composite material with these features can comprise tungsten, as the polyester of tackiness agent and the combination of zirconate interface modifier.End-use product can be the product of injection moulding or block mo(u)lded item.
A further embodiment of the invention is can be used for high yield, the high density composite in bait and automobile or truck inflation tire wheel counterbalance weight.Wheel balancing block comprises the goods block of annex and matrix material of the present invention.Counterbalance weight can connect with routine folder or adhere on wheel with tackiness agent.The exemplary composite material with these features can comprise tungsten, as the polystyrene of tackiness agent and the combination of zirconate interface modifier.End-use product can be the product of injection moulding or block mo(u)lded item.
Except foregoing example embodiment, other working method is but is not limited to: molding, compression moulding, thermoset and thermoplastic extrusion, centrifugal modling, rotational molding, blowing, casting, calendering, liquid filling thermoset molding or filament winding, to form different shape together with order mixture.Another embodiment of the present invention comprises the magnetic composition of gained matrix material, wherein in order to identify or as end-use requirement defined, add magnetic component.The weight and volume mark that magnetic additive accounts for gained matrix material is generally 0.1% to 5%.
A further embodiment of the invention comprises the painted of gained matrix material, wherein for identify or as end-use requirement defined color very important.The weight and volume mark that color additives accounts for gained matrix material is usually less than 1%.
Matrix material of the present invention can musket bullet or shaping round form be used in projectile.Musket bullet is generally spheroidal particle, is of a size of about 0.7 to about 3 millimeters and normally spherical, but can have drawn grain or pitted skin.
The projectile that can be used in the present invention comprises the high density composite of the present invention of suitable vast scale usually.Projectile can comprise the extrusion bar adding cover or do not add cover form.Chuck can surround matrix material, and maybe can to leave a part (front end or rear end) outside exposed.Matrix material can produce formation projectile in many ways.Projectile can comprise about 0.1 gram to nearly 2 kilograms of matrix materials of the present invention, described matrix material at least partly by metal chuck around.This kind of projectile can have cone-shaped open formula front end, open blind end or the two, or can be wholely encapsulated in chuck.In addition, chuck can comprise other assembly as explosive, ferrule or other insert, to change the Pneumatic pressure center of projectile or center of gravity or barycenter at the front portion of sized central or rear portion.This kind of projectile obtained by the matrix material comprising tungsten, iron or other nontoxic metal of the present invention forms " green " bullet or projectile, and it is degenerated to the non-toxic material compatible with animal with waterplant after a procedure.The elastic performance of material makes projectile particularly useful.Due to its high-density, projectile can transmit sizable inertia or kinetic energy to target, but the elastically deformable and make chuck expand as plumb when contacting equally.Chuck will expand by expection, but resilient material will recoil to its original dimension substantially.
Round or projectile can be designed to Pneumatic pressure center and center of gravity or barycenter can be regulated to the front portion of sized central or rear portion with the aeroperformance improving round.This kind of round can be fabricated to be avoided departing from desired trajectory and reducing accuracy with more stable ballistic flight.In addition, due to its stability, the emittance that material of the present invention can be higher is launched and is reduced weapon heat-dissipating because speed of rotation reduces.In preferred projectile of the present invention, before center of gravity is arranged in Pneumatic pressure center well, just the round of rotation is stabilized in its targeted trajectory.
In short, as herein the specific rights that comprises require pointed by, the present invention relates to a series of material combination, described material combination comprises metal, polymkeric substance, interface modifier and other additive, and it all has different particle diameters, weight fraction and volume fraction.The present invention also comprises the application of a series of working method, the physics and chemistry character of gained and end-use.Material below illustrates of the present invention.Described material all can be shaped, molding, extrude or make useful matrix material and shape.
Experiment 1
Experiment is made up of three main concern aspects: density, melt flow index, tensile strength and elongation.Density measurement produces sample by the device assembled with Wild River Consulting through expressing technique and carries out, and described device has 1 of the transformation in the hole of 0.1 inch diameter primarily of being equipped with in the metallurgical pressing machine of loadometer and underarm 1/ 4inch cylindrical die head forms.Suppose that the sample produced by these instruments is perfect right cylinder, therefore measure the density that mean diameter, length and quality just can obtain sample.
The melt flow index of each sample is measured in die head extrusion.Its rate of extrusion can be calculated by the time of the mark of working sample on instrument (instrument is by extruding lengthy calibration).Then this linear velocity normalization method is made divided by aperture.The amount of gained is defined as the melt flow index (MFI) of material.For guaranteeing to mix completely, the material extruded extrudes at least four times again.
Also test the tensile elongation that die head extrudes sample.Each sample is trimmed to 4 inches long, and apart from each end 1/ 2inch place marks.Sample is fixed in the fixture of instrument, wherein 1/ 2inch mark sample inserts the degree of depth in fixture.Carry out tension fracture test and take off sample in the completed.
In experiment, test uses two kinds of formulas of Alldyne C-60 tungsten and Dyneon THV220A fluoropolymer.The first formulating of recipe is for obtaining 10.8g/cm 3density.The second formulating of recipe is for obtaining 11.4g/cm 3density.Table 1 provides for the sample of generation two kinds formula weight percentage used.Four kinds of interface modifiers are tested in experiment.The first interface modifier is zirconium ester coupling agent NZ 12.Second and the third properties-correcting agent be titanate coupling agent KR238J and LICA09.Last a kind of interface modifier is silane SIA0591.0.
The different interface modifier of table 1 is on Composite Melt flowing and the impact of mechanical property
* the interface modifier of 0.2 % by weight is contained
Can be clear that, the process of tungsten powder causes the sizable change of physicals.In all formulas, the process of interface modifier affects melt flow significantly.The melt flow index of compounded materials is compared undressed compound and is increased up to 68 times.Also can see that it affects in the elongation of material.All four kinds of interface modifiers all cause the increase of tensile elongation, and wherein the change that causes of NZ 12 and KR238J is maximum.Although the material through SIA0591.0 process does not show the increase of melt flow index, it shows the increase of maximum stress really.The maximum stress that SIA0591.0 compounded materials produces be about not containing interface modifier 91.4 % by weight three times of tungsten compound.
Experiment 2,3 and 4
In table 2,3 and 4, tungsten particle first uses interface modifier process.This is undertaken by be dissolved in by interface modifier very in a small amount in the solvent (normal is Virahol or some other alcohol) in beaker and to mix with tungsten particle in beaker.Then gained slurry thoroughly mixes about 10 minutes.Basic decant goes out solvent or in about 100 DEG C of evaporation of solvent.Particle and then in an oven drying.Separately polymkeric substance (such as) THV220A is dissolved in solvent (as acetone).Then tungsten particle treated for suitable weight is added in the polymkeric substance of dissolving, stirs the mixture until most of solvent has evaporated and mixture is reunited.Material, in 100 DEG C of dryings 30 minutes, is then suppressed in metallurgical mould.
THV200A is the polymkeric substance of tetrafluoroethylene, R 1216 and vinylidene fluoride.NZ 12 is neo-pentyl (diallyl) oxygen base-three (dioctyl) phosphate-based (phosphato) zirconate.SIA0591.0 is N-(2-amino-ethyl)-3-aminopropyl-trimethyoxysilane.KR 238J is can from Kenrich Petrochemicals, the Methacrylamide modified amine adducts that Bayonne, NJ obtain.LICA 09 is neo-pentyl (diallyl) oxygen base-three (dodecyl) benzene-alkylsulfonyl-titanic acid ester.
The density of interface modifier on fluoropolymer matrix material of table 2 different concns and the impact of mechanical property
Table 3 interface modifier NZ 12 affects thermoplastic material (PVC) to PVC density polymer and mechanical property
Thermosetting material (polyester)
The annotation of table:
(1) one takes out and namely pulverizes from mould.
As seen from the table, multiple polymers can be used to preparation density higher than 10g/cm 3and there is useful viscoelastic matrix material.
The particle diameter of table 4 tungsten and circularity are on the impact of density
* containing NZ 12 interface modifier of 0.03-0.2%
These data in table show thermoplastic composite can with the preparation of selected combination of materials and the degree comprising the performances such as density, modulus, elongation can design in material.
This table shows that particle diameter, distribution and the circularity density on matrix material has impact.The preparation of these materials a-g is similar to embodiment 1-16.All samples in table 4 is all prepared as and makes formula produce the most highdensity matrix material.Owing to there is larger and little mean size particle materials and being about the smallest circular degree of 14, therefore material b and e has maximum density.In table, material a and c has low density and has little or large particle.(material b's and e) size that other material departs from a little or circularity parameter and density is reduced.
Experiment 5
Melt flow experimental data material therefor in table 5 is by following preparation.Technon Plus tungsten particle through modification, with Dyneon polymer blending being incorporated in forcing machine with the gravity-feeder through calibrating.Forcing machine be Brabender 0.75 inch band customization screw thread through transformation to produce low-compression single screw extrusion machine.Heating zone is set to 175 DEG C, 175 DEG C, 175 DEG C and 185 DEG C.Screw speed remains between 20 and 40rpm.Machine barrel is air-cooled.Material outlet speed is about 1 meter of per minute.Merged with the fluoropolymer DyneonTHV220 of 8 % by weight by the TechnonPlus tungsten (size distribution is 10 to 160 microns) of 92 % by weight in laboratory scale Brabender forcing machine, wherein Dyneon THV220 is the polymkeric substance with the modification of Kenrich NZ 12 zirconate interface modifier.In this embodiment, interface modifier with on metallic particles about 0.01 % by weight ratio be applied directly on tungsten particle.The typical melt flow index of material of the present invention is at least 5 seconds -1, at least 10 seconds -1, about 10-250 second -1or about 10-500 second -1.For measuring melt extrusion flow index, set up the pilot system of customization.Aperture (diameter 0.192cm) is bored in the metallurgical mould of 1.25 inches.Metallurgical mould combinationally uses with the metallurgical pressing machine being furnished with instrument, allows monitoring mould moderate pressure like this.The setting temperature of material and the pressure of mould, material is extruded by melt flow hole.For the given time length, measure the length of gained body, result is used for determining V-bar.Utilize this data, can melt flow index be calculated with the velocity contrast of extrudate divided by nib radius.
The affect density of material of table 5 temperature and pressure on melt flow is 11.2gm-cm -3(fluoroelastomer)
Articles Example
Production of articles embodiment 1
Contain: polystyrene, Technon powder, Kronos 2073 and Ken-React NZ 12.
Formula (by weight):
Polystyrene is dissolved in the mixture of toluene, methylethylketone and acetone to total solids be 38 % by weight.Under stirring, two kinds of Granular composite are added NZ 12 in identical solvent mixture in this dispersion.TiO is opened in stirring 2add polystyrene solution after reunion and stir and discharge solvent until blend becomes semisolid simultaneously.Then this material is compression molded into the fishhook (see Fig. 3) of band No. 1 hook.
Production of articles embodiment 2
Contain: polystyrene, Technon powder and Ken-React NZ 12.
Formula (by weight):
Polystyrene 0.6011g
Technon PLUS particle 12.0927g
Ken-React NZ 12 0.03g＊
Polystyrene is dissolved in the mixture of toluene, methylethylketone and acetone to total solids be 38 % by weight.Under stirring, W Granular composite is added NZ 12 in identical solvent mixture in this dispersion.Add polystyrene solution and stir and discharge solvent until blend becomes semisolid simultaneously.Then this material is compression molded into sliding pendant (slip sinker).
Production of articles embodiment 3
Contain: polyester, Technon powder, Kronos 2073 TiO 2with Ken-React NZ 12.
Formula (by weight):
Methylethyl ketone peroxide
Polyester is added to W and TiO 2in particle.Add acetone to disperse to help NZ 12.Start to occur colour developing sign (i.e. TiO at blend 2dispersion) after, add more acetone, then add methylethyl ketone peroxide.This material is compression molded into sliding pendant.
Production of articles embodiment 4
Contain: polyester, Technon powder, Kronos 2073 TiO 2with Ken-React NZ 12.
Formula (by weight):
Methylethyl ketone peroxide
Polyester is added to W and TiO 2in particle.Add acetone to disperse to help NZ 12.Start to occur colour developing sign (i.e. TiO at blend 2dispersion) after, add more acetone, then add methylethyl ketone peroxide.This material is compression molded into No. 1 sliding pendant.
Production of articles embodiment 5
Contain: fluoroelastomer, Technon powder and Ken-React NZ 12.
Formula (by weight):
Fluoroelastomer THV220A Dyneon 1.6535g
Technon PLUS particle 36.8909g
Ken-React NZ 12 0.0400g
Under the help of acetone by blended for NZ 12 enter in W particle.THV220A is dissolved in acetone to 38 % by weight, is then added in W slurry.Stir this blend to dry, then compression moulding in the metallurgical pressing machine of 1.25 inches.By this large pellet dice and in 104 DEG C of oven dryings to dry, then in metallurgical pressing machine in 5700lb/in 2with 177 DEG C at reshape.The density of this material is 11.7g/cm 3.
In these embodiments, tungsten particle is first through interface modifier process.This is undertaken by be dissolved in by the interface modifier of aequum in the 250ml beaker containing 50ml solvent (normal for Virahol or some other alcohol) and then to add 100 grams of tungsten particles in beaker.Gained slurry then in vapor bath thoroughly mixing until mixture can not stir again and most of solvent is displaced.Then the beaker containing tungsten particle and interface modifier is placed in the forced ventilation baking oven 30 minutes of 100 DEG C.The tungsten processed is added to and is dissolved in the 100ml beaker of the sosoloid in acetone containing THV220A.Then mixture is heated to 30 DEG C and continuously stirring until most of acetone evaporated.Then forced ventilation baking oven matrix material being placed in 100 DEG C reaches 30 minutes.Under the circuit die of 200 DEG C and 4.5 tonnes, matrix material is suppressed in 3.17cm cylinder after drying in metallurgical mould.Within 5 minutes, relief mould is cooled to 50 DEG C under stress.After relief pressure, from mould, take out composite sample and measure physicals.About composition and institute survey performance see show _.THV220A is the multipolymer of tetrafluoroethylene, R 1216 and vinylidene fluoride.NZ 12 is neo-pentyl (diallyl) oxygen base-three (dioctyl) phosphate-based zirconate.SIA0591.0 is N-(2-amino-ethyl)-3-aminopropyl-trimethyoxysilane.KR 238J is can from Kenrich Petrochemicals, the Methacrylamide modified amine adducts that Bayonne, NJ obtain.LICA 09 is neo-pentyl (diallyl) oxygen base-three (dodecyl) benzene-alkylsulfonyl-titanic acid ester.
Prepare a series of containing NZ 12 THV-220 of 0.1-0.2 % by weight and the exemplary materials of metallic particles as described above.
Table 6
The embodiment of various metal under different metal loading level
Monometallic matrix material
Double metallic composite material 90% maximum filling lower density=4.5
Table 6 provides a series of monometallic polymer composites that metal filled amount is 47-90 volume % metal.Different metal composites is provided to the composite density obtained by the metal polymer composite of the metal filled amount containing this percent by volume in each row of table.As seen from the table, for various metal, the density of matrix material is directly proportional to the percent by volume of this metal in matrix material.Such as, along with metal volume percentage composition or loading level increase to 90 volume % from 47 volume %, composite tungsten material density changes to about 18 from about 10, for each density metal increase similarly.
The volume graphically providing matrix material of the present invention in Figure 28,29 and 30 is filled and density characteristics.The volume drawing stainless steel, bismuth and composite tungsten material in Figure 28 fills the relation with density.Data source in Figure 28, from table 6, shows that density fills linear increasing, as data prediction from table relative to volume.The relation of metal volume percentage ratio in the final densities of zinc, palladium, copper, tantalum, osmium, stainless steel, bismuth and composite tungsten material and matrix material is drawn in Figure 28.Equally, as from table, (data in table 6) are predicted, the density of matrix material increases with the increase of metal volume percentage ratio in matrix material.Figure 30 shows with about 45% until the volume of about 90% fills the maximum density obtaining matrix material of the present invention.The maximum density obtained is about 20-21g/cm.
We are by material property inspection and instrument analysis technology evaluation, the heat measuring and characterize two kinds of metal polymer composites of the present invention and visco-elasticity.These performances have no in the prior art.Generally, prior art material fails to obtain true composite characteristics, therefore can not obtain true viscous-elastic behaviour and the thermal conduction characteristic of true matrix material.This kind of material is crisp, can not extrusion molding or injection moulding and high heat conduction level can not be reached.
The thermal characteristics of material of the present invention is unique.Although described material is metal polymer composite, the thermal characteristics of this matrix material more as metal, instead of more as polymkeric substance.When being used in heat transfer applications, thermal conductivity can be greater than 1W-M -1° K -1and can be 50-175W-M -1° K -1, 75-155W-M -1° K -1or 87-105W-M -1° K -1.Available operating temperature range is about-50 DEG C to about 130 DEG C.
For visco-elasticity, use tensile elongation and slit die rheological technique.Viscosity is determined in melt-processed process is undertaken by the Han slit die be contained on Haake singe screw torque rheometer.The viscoelastic sign extruding sample is completed by Chatillon LFPlus uniaxial tensile elongation rate tester.The object of experiment is also attempted setting up difference that between two kinds of matrix materials, viscosity/viscoelasticity can characterize or is confirmed that bi-material has identical viscosity/viscoelasticity.The bi-material of comparing has similar formulation but prepares the composite tungsten material different with work-ing life.
Matrix material discussed below is used in characterization.Two kinds of matrix materials are prepared substantially as mentioned above and use the interface modifier of about 0.1-0.2 % by weight.The material analyzed in Table A-H and Figure 12-20 forms primarily of tungsten or other metallic particles and THV220, and density is 11.4g/cm 3, it corresponds to two kinds of matrix materials containing about 56 volume % tungsten powders.The Main Differences of storeroom is that a kind of material is by tungsten and THV220 only mixture once granulating, and another material is by working cycle mixture.Working cycle is made up of multi-step process, wherein the formation of material at least comprise the steps: by be pellet through the tungsten of interface modification and THV220 mixture, with painted THV220capstock coextrusion, shred in tablets press, mixture returns pellet and with tungsten mixture to obtain specific density.Only mixture material once will be called as " starting materials ", and the material of multistep mixture will be called as " reprocessing material ".This shows that starting materials has unique heat and viscous-elastic behaviour and reprocessing material has identical performance.
Make the about 800ml loose material of each matrix material respectively by Haake torque rheometer.Haake rheometer has internal diameter to be the bobbin of an inch and to be all set as three humidity provinces of 140 DEG C.On torque rheometer, connect Han slit die, this slit die has the shaping segment lenght of square-section and about 75 being about 2.0mm × 20.00mm, the rheometer pressure of melt stream in three determination of pressure sensor extrusions.Connect two heating zones to seam place, the set(ting)value of the two all controls to be 140 DEG C.Haake slit die software is by measuring the shear-stress of the Pressure Drop Calculating material along inner three points of slit die.Slit die software requirement is extrusion test program input lower limit and the upper limit.The lower limit of RPM is set to 5rpm, and the upper limit is set to 100rpm.Then Haake software select 8 rpm set(ting)values to share 10 rpm set(ting)values in test procedure between bound.The technological operation scope that span is wider more than the screw rod range of set value representative of an order of magnitude.Rheometer automatically can run under each rpm set(ting)value.When Haake is when extruding, cut extrudate generation sample afterwards in extruding 60 seconds.Then weigh sample extrudate weight and by gained weight typing Haake.Utilize the volume output valve of composite density by each rpm set(ting)value of computed in software of the example weight of input and previous input.Note, software does not allow to input 11.4g/cm 3this density, thus input 1.14 these values, therefore all samples weight input value all divided by ten with compensation density scalar.Software volume output valve calculates the shearing rate in slit die.
After all screw speed set(ting)values all complete, run Haake evaluation software, original output is transfused in electronics trial balance then to the map data collected.Be 11.4g/cm by Haake software and operator 3starting materials the first round collect raw data.Listed rpm set(ting)value is selected by Haake software, except minimum and maximum value.Pressure 1,2 and 3 is measured by the melt force sensor being arranged in Han die slot.Before screw head place enters slit die, the melt pressure of material is by the determination of pressure sensor being labeled as P0.Shaft torque and melt temperature are by Haake rheometer measurement.Mass flow rate is by the 60 seconds sample determinations got in extrusion.Volumetric flow rate mass flow rate is divided by density calculation.
Table A
For analyzing 11.4g/cm 3starting materials, by Haake computed in software output valve.Shearing rate, shear-stress and viscosity are calculated by the value presented in Haake software table B.
Table B
Be second take turns 11.4g/cm by Haake software and operator 3starting materials collect raw data.Listed rpm set(ting)value is selected by Haake software, except minimum and maximum value.Pressure 1,2 and 3 is measured by the melt force sensor being arranged in Han die slot.Shaft torque and melt temperature are by Haake rheometer measurement.Mass flow rate is by the 60 seconds sample determinations got in extrusion.Volumetric flow rate mass flow rate is divided by density calculation.Notice that some values are without Haake software records or display, be not therefore presented in table C.
Table C
For second time analyzes 11.4g/cm 3starting materials, by Haake computed in software output valve.Shearing rate, shear-stress and viscosity are calculated by the value presented in Haake software table D.Notice that the value lacked in table D causes the blank in this table.
Table D
Be third round 11.4g/cm by Haake software and operator 3starting materials collect raw data.Listed rpm set(ting)value is selected by Haake software, except minimum and maximum value.Pressure 1,2 and 3 is measured by the melt force sensor being arranged in Han die slot.Shaft torque and melt temperature are by Haake rheometer measurement.Mass flow rate is by the 60 seconds sample determinations got in extrusion.Volumetric flow rate mass flow rate is divided by density calculation.
Table E
For third time analyzes 11.4g/cm 3starting materials, by Haake computed in software output valve.Shearing rate, shear-stress and viscosity are calculated by the value presented in Haake software table F.
Table F
By Haake software and operator be analyze 11.4g/cm 3reprocessing material collection raw data.Listed rpm set(ting)value is selected by Haake software, except minimum and maximum value.Pressure 1,2 and 3 is measured by the melt force sensor being arranged in Han die slot.Shaft torque and melt temperature are by Haake rheometer measurement.Mass flow rate is by the 60 seconds sample determinations got in extrusion.Volumetric flow rate mass flow rate is divided by density calculation.Notice that some values are without Haake software records or display, are not therefore presented in table.
Table G
For analyzing 11.4g/cm 3reprocessing material, by Haake computed in software output valve.Shearing rate, shear-stress and viscosity are calculated by the value presented in Haake software table H.
Table H
Figure 12 is to 11.4g/cm 3original and reprocessing material provide the mass flow rate calculated value (g/min) of extrudate under different screw speed (rpm).The data that starting materials is respectively taken turns take from Table A, C and E.The data of reprocessing material take from table G.
Figure 13 is to 11.4g/cm 3original and reprocessing material provide different screw speed (rpm) under be applied to torque value (Nm) on screw rod.The data that starting materials is respectively taken turns take from Table A, C and E.The data of reprocessing material take from table G.
Figure 14 is to 11.4g/cm 3original and reprocessing material provide the shearing rate calculated value (1/s) of material in extrusion under different screw speed (rpm).The data that starting materials is respectively taken turns take from table B, D and F.The data of reprocessing material take from table H.
Figure 15 is to 11.4g/cm 3starting materials provide the melt pressure observed value of material in extrusion under different screw speed (rpm).Above a class value correspond to P1 sensor, below a class value correspond to P3 sensor.The data that starting materials is respectively taken turns take from table B, D and F.The data of reprocessing material take from table H.
Table 16 couple 11.4g/cm 3starting materials provide the shear-stress calculated value (Pa) of material in extrusion under different screw speed (1/s).The data that starting materials is respectively taken turns take from table B, D and F.The data of reprocessing material take from table H.
Figure 17 is to 11.4g/cm 3starting materials provide the apparent viscosity calculated value (Pa*s) of material in extrusion under different screw speed (1/s).The data that starting materials is respectively taken turns take from table B, D and F.The data of reprocessing material take from table H.
Figure 18 is to 11.4g/cm 3starting materials be given in the shear-stress calculated value (Pa) of material in extrusion under the shearing rate (1/s) of calculating.The data that starting materials is respectively taken turns take from table B, D and F.The data of reprocessing material take from table H.
Figure 19 is to 11.4g/cm 3starting materials be given in the apparent viscosity calculated value (Pa*s) of material in extrusion under the shearing rate (1/s) of calculating.The data that starting materials is respectively taken turns take from table B, D and F.The data of reprocessing material take from table H.
Figure 12 provides and takes turns the stress (MPa) of the tensile elongation of the sample of starting materials and reprocessing material wheel and strain (%) result from first and second.The sample extruded is cut into ASTM638-4 dog bone-shaped sample and stretches until rupture failure with 25mm/min.
As shown in Figure 12, the mass flow rate of extrudate is for screw speed until the situation of 40rpm is roughly the same, and described mass flow rate is extruded the length of material of 60 seconds time length by cutting and recorded.Same from Figure 12, for the situation of screw speed higher than 40rpm, the mass flow rate between each wheel starts difference.The all three-wheels noting the original composite material of 11.4 are all tested under independently occasion from the material of same batch.The change of extrusion material quality flow most likely due to when forcing machine speed increases material spill that mould rear portion causes.More specifically, material spills the joint between forcing machine and Han slit die.Along with screw speed increases, more materials are had to spill.Leaking material takes turns the most outstanding at the 2nd and 3 of starting materials.
Due to for three-wheel starting materials, the mass rate of material is inconsistent with associating of screw speed with volumetric flow rate subsequently, therefore the value deriving from volumetric flow rate in three-wheel also should not be relevant to rpm.This non-correlation explains the difference of respectively to take turns a shear-stress, shear strain and apparent viscosity when mapping to screw speed.The shortage of this dependency can be seen in Figure 14 and 17.
11.4g/cm 3the result that provides of reprocessing matrix material and 11.4g/cm 3original composite material the 1st take turns the most alike.As shown in Figure 12, under given flow rate, the mass flow rate of material is taken turns between starting materials the most similar at reprocessing material and the 1st.As shown in Figure 14, described material is also similar by the shearing rate subsequently of Han slit die.
The torque all similar between all each wheels on screw rod is applied in extrusion.Although Fig. 2 shows all material all similar, between respectively taking turns during 40rpm, there is fine difference at screw speed.
As can be seen from Fig. 15, bi-material all shows Pressure Drop identical in depanning.Three starting materialss and reprocessing storeroom do not have visibly different pressure gap trend or amplitude.The calculating of the 1st and 2 shear-stresses of taking turns is by manually completing, and reason is the calculating that evaluation software is done is carry out with the sensor that mistake is specified.1st and 2 take turns with sensor P0, P1 and P3, and the 3rd takes turns with sensor P1, P2 and P3.Notice that P0 is the sensor after mould, P1 is the first pressure spot in mould, and P2 is the second pressure spot in mould, and P3 is the 3rd pressure spot in mould.Pressure spot P0 is not positioned at slit die, therefore can not be used for calculating the Pressure Drop crossing over seam.Value due to P0 is at least the twice of P1 value, therefore shear stress values can than right height.3rd takes turns as right value, and reason is that it carries out calculating based on the Pressure Drop crossing over mould and does not use recorded P0.
The 11.4g/cm provided in table B and D 3the 1st and 2 apparent viscosity results of taking turns of starting materials manually determine, reason specifies P0 as one of pressure in the calculating of evaluation software.3rd takes turns and provides accurate viscosity output valve, and it can find in table F, and it is almost overlapping with the analog value of the reprocessing material of visible 11.4 in table H.Relation between apparent viscosity and screw speed can be seen in fig. 17.There are differences between each wheel, this is that because mould joint leaks material, relation between the screw speed that causes and shearing rate is inconsistent causes due to above-mentioned.When directly mapping to shearing rate with apparent viscosity, as in Figure 19, observe all four groups of data all overlapping.Between described three-wheel starting materials and reprocessing material wheel, the measurement capability of method do not have marked difference.As shown in Figure 18, the shear-stress of storeroom and shearing rate there are differences.All each wheel except second of starting materials is taken turns follows similar trend.
Tensile elongation that is original and reprocessing storeroom is very close.As shown in Figure 20, the stress-strain behavior of each material is difficult to differentiate each other.Although the breaking strain % of reprocessing material seems obviously lower, the difference strained between same sample is approximately ± and 25%.Stress along strain paths is more identical for all each wheels.Experiment proves that the viscosity of bi-material and visco-elasticity all can characterize.But in measurement capability original and reprocessing composite tungsten material between there is no difference.This shows that the recombination property of material is the essential property of matrix material, can't simply because extrude material again or reprocess and lose.
One of key physical properties that every class material is surveyed is the relation between the distortion that is applied to power on material and this power and causes.The ad hoc fashion of the power applied under this situation is the uniaxial extension of the linear deformation under constant rate of speed.Because sample extends because of applied drawing force in the process, so performance test is often called " tensile elongation " simply.The object of presents limits the key parameter of tensile elongation test method and analysis, then compares the performance of two kinds of matrix materials.
Can be this test method and define some Key Terms.Figure 21 is the typical curve of material property with regard to stresses typical-coping behavior under tensile elongation, and it does crooked for illustrative purpose.
First term of definition is stress (σ), and it is be applied to the power on sample to amass divided by the initial cross sectional of sample.The power be applied on sample is single shaft, axial vertical (bidimensional is all vertical) of cross section and power.
Second term of definition is strain (ε), and it is that the increase of sample length is divided by initial sample length.This amount is often expressed as percentage ratio, and the sample being wherein in 100% strain is the twice of its initial length.
3rd term of definition is the ε in Figure 21 ain letter " A ".After the opposite linear part of stress-strain curve, sharply decline irreversible deformation by sample of stress causes.The stress value at this some place is defined as upper yield stress.Although the acutance at this peak of sample room may be different, that define this value is local maximum (local maxima).
4th term of definition is the ε in Figure 21 bin letter " B ".After the upper yield point caused by irreversible viscous deformation, the stress maintained needed for constant strain speed starts to increase at leisure.The stress value at local minimum (local minima) place produced is defined as lower yield stress.After this point, stress level starts to rise, usually linear increase.
5th term of definition is the ε in Figure 21 cin letter " C ".Destroy sample stress when (fracture) starts and can present another local maximum.This point is defined as rupture stress, often for being applied to the maximum stress level on sample.Due to the amount that it is the stress caused needed for destruction, therefore it is often called as " tensile strength " of material.
6th term of definition is the ε in Figure 21 din letter " D ".When sample breakage, applied force is vanishing immediately.The deformation values at this some place is defined as breaking strain %.
7th term of definition is the ε in Figure 21 ein letter " E ".Before surrender, stress and strain is the relation of substantial linear.This part distortion makes material show as elasticity just.This line is defined as the Young's modulus of material with the slope of unit of stress or is called for short modulus.In these data, term sequence ε a, ε brefer to a series of strain points that strain % increases; ε a< ε b; ε c< ε ddeng.Showing this characteristic material is true matrix material, obtains the best visco-elasticity of polymkeric substance and the density, thermal characteristics, electrical property etc. of metallic particles.Although the packing material of prior art is fine and close but do not have such viscous-elastic behaviour or thermal property.
The material that test two kinds is different in tensile elongation process.The first material is the tungsten of NZ-12 interface modification and the matrix material of THV220.The particle shape of tungsten is subcircular but irregular and rough and uneven in surface.Formula contains the treated metal powder of 60 volume %, its approximately low than closest packing 1 volume %.With regard to the object of this experiment, the formula in 1 volume % of closest packing will be called as the closest packing (functional closest packing) worked.The density of this material is about 11.9g/cm 3.
The second material is the 316L stainless steel of NZ-12 interface modification and the matrix material of THV220.Stainless particle shape is spherical (aerosolization), containing some association particles, does not almost have anomalistic object.Formula contains the treated metal powder of 62 volume %, and it is also prepared with closest packing.The density of this material is about 5.5g/cm 3.
Two samples are all by being furnished with the diameter 1 of 3mm × 20mm rectangle pattern " single screw extrusion machine extrude.The condition of forcing machine is about 135-145 DEG C and 1000psig.The band being about 6 inches extruded separately is used for punching press ASTM 638-4 dog bone-shaped sample to carry out tensile elongation test.Dog bone-shaped sample characteristics is gauge length is 1.75 inches, gage width is 0.25 inch.Gauge-thickness determines by extruding thickness, is about 3.0cm.Each sample is arranged on instrument and also tests respectively.Constant rate of deformation is 25mm/min.Take off sample after rupture failure, test completes.
Table I
Characterize the key value of tested composite tungsten material and stainless steel composite material stress-strain behavior
Stress value at tungsten and stainless steel composite material tensile elongation duration of test differently strained some place has separately been shown in Figure 22.The about poor twice of amount of the stress needed for two kinds of subject material chien shih subject material distortion.As visible in Table I and Figure 22, the stress value of composite tungsten material is higher than the value of stainless steel composite material.Although stress value differs 2 times, Curve total between stress and strain and relation are similar.No matter how the composition of particle all can obtain visco-elasticity.
From lower yield point to fracture, the linear increase of stress is roughly the same for bi-material, and difference is within 1.5 times.The breaking strain % of bi-material, in the range of uncertainty measured, is about 425 ± 25% strains.The maximum value of two sample room difference is Young's modulus.The difference on the order of magnitude is there is between bi-material.Although this difference is large, the rate of deformation of the ASTM Guidelines recommend measured about tensile modulus is the 25mm/min adopted in 1mm/min instead of this experiment.
Figure 23 and 24 is the magnification region of Figure 22.Their data are identical, just illustrate initial slope and the yield value of material.
Figure 25 illustrates the visco-elasticity of THV fluoropolymer material of the present invention.Data in curve are from following table J.
Table J
Although the stress-strain(ed) curve of polymkeric substance and the somewhat similar of matrix material, can find out that the interpolation of metal enhances initial modulus and remains cumulative strain curve and suddenly change at the level place reduced.
Tested characterize each material and be associated with production technique and end article performance to the performance of stainless steel composite material.Matrix material by produce shown in above and contain 0.5 % by weight IM.For each supplying material provides the representative value of listed each character.Tested characterize each material and be associated with production technique and end article performance to the performance characteristics of the material of supply.For each supplying material provides the representative value of listed each character.Prepare injection moulded embodiment, material is as follows:
Table K
* IM is containing heavy by 0.5%
* IM content 0.15%
Injection moulding performance is:
Table L
Even if the smooth injection moulding of material shows containing vast scale or more than half (in weight or meausurement) material in metallic particles form in the material for true VISCOELASTIC FIBER COMPOSITES, described matrix material also available standards is extruded or injection moulding is thermoformed into useful product.
For confirming the impact not obtaining true composite characteristics, carry out tensile elongation mensuration to two kinds of matrix materials containing 62 volume % metals, a kind of matrix material is containing the powder of interface modification, and another kind of matrix material is not containing the powder of interface modification.ASTM 638-4 type dog bone-shaped sample analysis all used by two kinds of matrix materials.By to containing and not containing the stainless matrix material of interface modification analysis in collect critical data.
Table M
Figure 26 and 27 shows do not have useful performance containing matrix material during IM material.NZ12 with 0.4% carries out to stainless steel the tensile property that interface modification changes matrix material, makes material become the true matrix material of the flexible that can extend from fragility packing material.Through nearly 100 times that the breaking strain % of the matrix material of interface modification is the matrix material without interface modifier.
Discussing in detail of some accompanying drawing
Fig. 1 shows the stereographic map of the support comprising metal polymer composite of the present invention.Support can be carved by the molded tube of matrix material known machinery or laser method, or support can directly be molded as shown form.Support 10 can comprise matrix material and have compliant member 11, and compliant member 11 makes support easily extensible when being placed in vessel lumen.Support has bending part 13 and linear element 12, and it can be formed by direct molding technique or by being carved described structure by molded tube by matrix material.
Fig. 2 A show there is symmetrical appearance extrude parts.Extrude object 20 and there is main body 21 containing plug-in unit 23A and symmetrical grooves 24A.Suitable length be extruded and be cut into such structure 20 can, then each length can with symmetrical parts mating, so that plug-in unit 23A can inject in groove 24B while plug-in unit 23B is injected groove 24A, main body 21 and main body 22 is made to interlock the assembly forming fixing mechanically stable.This assembly illustrates in fig. 2b.The object of filling substantially completely in whole molectron is defined in Fig. 2 A.
Fig. 3 shows two kinds of fishhooks 30 and 31.Described fishhook comprises hook 32,33.Hook is equipped with and fishes pendant 34,35.Fish pendant 34 to fish pendant for molded, formed on hook 33 by compression moulding.Fish pendant 35 to be that the press-fit similar to the extrudate of Fig. 2 fishes and fall, comprise the plug-in unit for snap-on fit structure and groove.
Fig. 4 shows the structure of two kinds of wheel balancing blocks of the present invention.In Figure 4 A, wheel balancing block 40 comprises forming blocks 44 of the present invention, and forming blocks 44 has can connect the adhesive strip 45 of counterbalance weight on wheel.Described counterbalance weight can be extruded with the form of continuous sheet material and be cut into forming blocks 44, and buckled zone 46 is formed before cutting in counterbalance weight 44.This matrix material is flexible, flexible to meet wheel shape shape.Fig. 4 B shows the counterbalance weight 41 with composite block 42 and machinery folder 43, and machinery folder 43 is configured to the wheel being connected to carrier vehicle.
Although specification sheets above provides feasible disclosing to composite technology of the present invention, also other embodiment of the present invention can be implemented without departing from the spirit and scope of the present invention.Correspondingly, the present invention embodies in subsidiary claims.
Remarks
The invention still further relates to following embodiment.
1. a VISCOELASTIC FIBER COMPOSITES for metal and polymkeric substance, described matrix material comprises:
(a) metallic particles, its particle diameter makes the described particle lower than 5 % by weight be less than about 10 microns, and the amount of described particle accounts for about 45 to about 95 volume % of described matrix material; With
(b) polymer phase, described polymer phase accounts for about 5 to about 55 volume % of described matrix material,
Wherein when being subject to deformation force, described VISCOELASTIC FIBER COMPOSITES indicating characteristic stress-strain curve, described curve has at ε athe yielding stress maximum value A at place, at ε bthe lower yield stress mnm. B at place, at ε cplace the second yielding stress maximum value and break apart initial point C, at ε d0 strain at place destroys D, the ε of described matrix material dbe greater than 10%, the increase of each ε representative strain %.
2. according to 1 matrix material, wherein said stress point A is higher than 0.2MPa.
3. according to 1 matrix material, wherein said stress point B is lower than 60MPa.
4. according to 1 matrix material, wherein said stress point C is higher than 0.2MPa.
5. according to 1 matrix material, the volume of wherein said metallic particles is filled and is greater than 45 volume %.
6. according to 1 matrix material, the volume of wherein said metallic particles is filled and is greater than 54 volume %.
7. according to 1 matrix material, wherein said polymkeric substance is that density is greater than 1.3g/cm 3polymer containing halogen.
8. according to 1 matrix material, wherein said matrix material comprise account for described matrix material about 0.0005 to about 2 % by weight interfacial modifier material;
9. according to 1 matrix material, wherein said matrix material comprise account for described matrix material about 0.0005 to about 1 % by weight interfacial modifier material;
10. according to 1 matrix material, wherein said metallic particles comprise have about 10 to 70 micron grain sizes distribution metal.
11. according to 7 matrix material, wherein said metallic particles comprises the metal that at least 5 % by weight particle diameters are about 70 to 250 microns.
12. according to 4 matrix material, wherein said polymkeric substance comprises density and is greater than 1.7g/cm 3fluoropolymer.
13. according to 1 matrix material, the excluded volume of wherein said metallic particles is about 20% to about 55 volume % and described metal exists with the amount of about 95-96 % by weight.
14. according to 2 matrix material, wherein said stress point A is positioned at about 1-10MPa place.
15. according to 3 matrix material, wherein said stress point B is positioned at about 1-10MPa place.
16. according to 4 matrix material, wherein said stress point C is positioned at about 1-10MPa place.
17. according to 1 matrix material, wherein said metallic particles comprises at least about 10 % by weight at the particle of particle and at least 5 % by weight scope more than about 250 microns of about 70 to 250 micrometer ranges.
18. according to 1 matrix material, wherein said polymkeric substance comprises density for about 1.8g/cm 3fluoropolymer.
19. according to 1 matrix material, wherein said metal comprises tungsten.
20. 1 kinds of heat transfer structures, described structure comprises:
(a) thermal source;
(b) heat transfer layer; With
(c) heated structure;
Wherein said heat transfer layer comprises metal and polymer viscoelastic matrix material, described matrix material comprises metallic particles, polymer phase and interface modifier, the particle diameter of described metallic particles makes the particle lower than 5% be less than about 10 microns, and the amount of described particle accounts for about 45 to about 95 volume % of described matrix material; Described polymer phase accounts for about 5 to about 55 volume % of described matrix material; Described interface modifier accounts for about 0.005 to about 2 % by weight of described matrix material; And the thermal conductivity of described heat transfer layer is higher than about 1W-M -1° K -1.
21. according to 20 heat structure, wherein said thermal conductivity is about 50 to about 175W-M -1° K -1.
22. according to 20 heat structure, wherein said thermal conductivity is 75-155W-M -1° K -1.
23. according to 20 heat structure, wherein said thermal conductivity is about 87-105W-M -1° K -1.
24. according to 20 structure, the useful working range of wherein said composition is about-50 DEG C to about+130 DEG C.
25. according to 20 heat structure, the circularity of wherein said metallic particles is greater than 14, density is greater than 5-21g/cm 3.
26. according to 20 heat structure, wherein said composite density is greater than 8-12g/cm 3.
27. according to 20 heat structure, wherein said polymkeric substance is that density is greater than 1.7g/cm 3polymer containing halogen.
28. according to 20 heat structure, wherein said matrix material comprises the tinting material of about 5 % by weight.
29. according to 28 heat structure, wherein said tinting material comprises pigment, dyestuff, fluorescence dye or its mixture.
30. according to 20 heat structure, wherein said metallic particles comprise have about 10 to 70 micron grain sizes distribution tungsten.
31. according to 20 heat structure, wherein said metallic particles comprises tungsten, and described tungsten at least 5 % by weight particle diameter is about 70 to 250 microns.
32. according to 20 heat structure, wherein said polymkeric substance comprises fluoropolymer.
33. according to 20 heat structure, the excluded volume of wherein said metallic particles is about 20% to about 55 volume % and described metal exists with the amount of about 70-95 % by weight.
34. according to 20 heat structure, wherein said metallic particles comprises at least about 10 % by weight at the particle of particle and at least 5 % by weight scope more than about 250 microns of about 70 to 250 micrometer ranges.
35. according to 20 heat structure, wherein said polymkeric substance comprises fluoropolymer.
36. according to 20 heat structure, wherein said metal comprises tungsten.
37. according to 20 heat structure, wherein said metallic particles comprises bismuth, and described bismuth at least 5 % by weight particle diameter is about 70 to 250 microns.
38. according to 20 heat structure, wherein said metallic particles comprises ferrous metal, and this ferrous metal at least 5 % by weight particle diameter is about 70 to 250 micrometer ranges.
39. according to 38 heat structure, wherein said metallic particles comprises stainless steel.

Claims (20)

1. a VISCOELASTIC FIBER COMPOSITES for metal and polymkeric substance, described matrix material comprises:
A () metallic particles, comprises the metallic particles that particle diameter is greater than 10 microns, the amount of described metallic particles accounts for 40 to 96 volume % of described matrix material, and described particle comprises the external coating (EC) of interface modifier; With
(b) polymer phase, described polymer phase accounts for 4 to 60 volume % of described matrix material,
Wherein said polymkeric substance is before being incorporated to described VISCOELASTIC FIBER COMPOSITES, and when described polymkeric substance is subject to stretching force to initial collapse, indicating characteristic stress-strain behavior, comprises upper yield stress, lower yield stress and rupture stress; With
Wherein said VISCOELASTIC FIBER COMPOSITES is when being subject to stretching force to initial collapse, and described VISCOELASTIC FIBER COMPOSITES is indicating characteristic stress-strain behavior also, comprises upper yield stress, lower yield stress and rupture stress.
2. matrix material as claimed in claim 1, wherein when described VISCOELASTIC FIBER COMPOSITES is extruded again or reprocess and be subject to stretching force subsequently to initial collapse, described VISCOELASTIC FIBER COMPOSITES is indicating characteristic stress-strain behavior also, comprises upper yield stress, lower yield stress and rupture stress.
3. matrix material as claimed in claim 2, wherein the matrix material of virgin state has heat with viscoelastic property and the identical matrix material of reprocessing state has identical heat and viscoelastic property.
4. a VISCOELASTIC FIBER COMPOSITES for metal and polymkeric substance, described matrix material comprises:
A () metallic particles, comprises the metallic particles that particle diameter is greater than 10 microns, the amount of described metallic particles accounts for 40 to 96 volume % of described matrix material, and described particle comprises the external coating (EC) of interface modifier; With
(b) polymer phase, described polymer phase accounts for 4 to 60 volume % of described matrix material,
Wherein said polymkeric substance is before being incorporated to described VISCOELASTIC FIBER COMPOSITES, and when being subject to deformation force to initial collapse, indicating characteristic stress-strain(ed) curve, described curve has at ε athe yielding stress maximum value A at place, at ε bthe lower yield stress mnm. B at place, and at ε cthe second yielding stress maximum value C at place; With
Wherein said VISCOELASTIC FIBER COMPOSITES is when being subject to deformation force to initial collapse, and indicating characteristic stress-strain curve, described curve has at ε athe yielding stress maximum value A at place, at ε bthe lower yield stress mnm. B at place, and at ε cthe second yielding stress maximum value C at place.
5. matrix material as claimed in claim 4, wherein the matrix material of virgin state has heat with viscoelastic property and the identical matrix material of reprocessing state has identical heat and viscoelastic property.
6. the matrix material as described in claim 4 or 5, the wherein described yielding stress maximum value ε at stress point A place ahigher than 0.2MPa.
7. matrix material, the wherein described yielding stress maximum value ε at stress point A place as claimed in claim 6 afor 1-10MPa.
8. the matrix material according to any one of claim 4 to 7, the wherein described yielding stress mnm. ε at stress point B place blower than 60MPa.
9. matrix material, the wherein described yielding stress mnm. ε at stress point B place as claimed in claim 8 bfor 1-10MPa.
10. the matrix material according to any one of claim 4 to 9, the wherein described yielding stress maximum value ε at stress point C place chigher than 0.2MPa.
11. matrix materials as claimed in claim 10, the wherein described yielding stress maximum value ε at stress point C place cfor 1-10MPa.
12. as matrix material in any one of the preceding claims wherein, and wherein said metallic particles comprises iron, tungsten, copper, or its alloy, or its mixture, and volume filling is greater than 54 volume %.
13. as matrix material in any one of the preceding claims wherein, and wherein said polymkeric substance is that density is greater than 1.3g/cm 3polymer containing halogen.
14. matrix materials as claimed in claim 13, wherein said polymer containing halogen comprises density and is greater than 1.7g/cm 3fluoropolymer.
15. as matrix material in any one of the preceding claims wherein, wherein said matrix material comprise account for described matrix material 0.1 to 1 % by weight interfacial modifier material.
16. matrix materials as claimed in claim 15, wherein said matrix material comprise account for described matrix material 0.1 to 0.5 % by weight interfacial modifier material.
17. as matrix material in any one of the preceding claims wherein, and wherein said metallic particles comprises the metal with 10 to 70 micron grain size distributions.
18. as matrix material in any one of the preceding claims wherein, and the excluded volume of wherein said metallic particles is 20% to 55 volume % and described metal exists with the amount of 95-96 % by weight.
19. as matrix material in any one of the preceding claims wherein, and wherein said composite density is greater than 5g/cm 3.
20. 1 kinds of wheel balancing block goods, comprise as matrix material in any one of the preceding claims wherein.
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