CN105001661B

CN105001661B - The metal polymer composite of viscoplasticity and hot property with enhancing

Info

Publication number: CN105001661B
Application number: CN201510266702.9A
Authority: CN
Inventors: 库尔特·E·海基莱
Original assignee: Wild River Consulting Group LLC
Current assignee: Wild River Consulting Group LLC
Priority date: 2006-02-09
Filing date: 2006-02-09
Publication date: 2018-04-20
Anticipated expiration: 2026-02-09
Also published as: CN105001661A

Abstract

The present invention relates to viscoplasticity and the metal polymer composite of hot property with enhancing.The present invention relates to a kind of metal polymer composite in the composite with enhancing or the performance improved.The performance includes viscoplasticity, color, magnetism, thermal conductivity, electric conductivity, density, improved ductility and toughness and thermoplasticity or injection moldability.

Description

The metal polymer composite of viscoplasticity and hot property with enhancing

The application be the applying date on 2 9th, 2006, Application No. 200680053915.2, entitled " have and increase The divisional application of the Chinese patent application of strong viscoplasticity and the metal polymer composite of hot property ".

The application is as PCT International Patent Application on 2 9th, 2006 with applicant Wild River Consulting Group, LLC (state-owned enterprise of the U.S., to all designated states in addition to the U.S.) and applicant Kurt E.Heikkila (states of the U.S. The people, only to the U.S.) name submission.

Technical field

The present invention relates to viscoplasticity and the metal polymer composite of hot property with enhancing.In the composite material In, the new capability is strengthened by the new interaction of component.The metal polymer composite is not simply to mix Thing, but excellent machinery, electricity and other are obtained by the unique combination of scattered metal such as metallic particles and polymeric material Performance, wherein the unique combination optimizes the structure of composite material and characteristic by the way that polymer and the metal material of combination is blended To obtain true composite property.

Background technology

Will largely it focus on the composite material for creating unique energy.It is included in such material It is with the high density material for improving performance.For example, lead is commonly used in the application for needing high density material.High density material is answered With including musket bullet, other ballistic projectiles, bait, fishing pendant, wheel balancing block (weight) and other high-density applications.By In resistance to α, β and γ radiation, EMI and the ductility of lead, therefore lead is also used in answering for other performance of the needs in addition to density In, including in radiation shield.Lead snap on system fish pendant allow user easily will fish pendant pinch on fishline without Instrument or without big difficulty.In the case of musket bullet or other ballistic projectiles, lead provide required density, penetration power and Ductility is worn with obtaining good precision and minimum gun barrel.Lead has been to hunt and the main choosing in Military Application Select.It is well known that lead on the terminal use of bullet and projectile there are it is poisonous the shortcomings that.Due to lead concentration increase in lake and cause Natural Population is dead, and the U.S. and other local many jurisdiction of courts regions have thought better of or passed through and forbidden selling and make With plumb and plummet.Being equally used for the depleted uranium of projectile, there are machinability, toxicity and radiation problem.

For many years, it is generally multiple by obtaining preparing from the advantageous property of the two by two kinds of dissimilar combinations of materials Condensation material.True composite material is unique, because the interaction of material provides the optimum performance of two kinds of components.Many kinds are compound Material is known and not simple mixture.In general, the prior art thinks to combine certain form of gold with certain proportion Belong to the special performance that the alloy formed provides metal/metal alloy material.Obtained metal/ceramic composite is generally wrapped Include combination metal dust or fiber and the sinterable clay material into metal/ceramic composite.

Usual combined thermoplastic or thermosetting polymer phase and enhancing powder or fiber, generation is a certain range of to be filled material Material, true polymers composite material can be formed under the conditions of appropriate.Filled polymer with the additive as filler cannot Show composite property.Filler generally comprises the inorganic material as pigment or extender for polymeric system.It is logical Often obtained multiple fiber strengthens composite material to obtain the fiber reinforcement of the mechanical performance of polymer in the unique composite material of improvement Performance.

One subclass of fill polymer material is that wherein metal material, metallic particles or fiber disperse in the polymer Metal-containing polymer mixture.Most of such materials are mixture rather than true composite material.Mixture usually can easily divide From for component and showing the performance of component.True composite material, which is resisted, separates and shows the enhancing performance of input material.It is very multiple Condensation material does not show the performance of each component.The United States Patent (USP) No.3,895,143 of Tarlow teaches one kind and includes elastomer The plate of latex, the elastomer latices include scattered inorfil and metallic particles.The United States Patent (USP) of Bruner et al. No.2,748,099 teach a kind of nylon material containing copper, aluminium or graphite, and the copper, aluminium or graphite are used to change material Heat or electrical property rather than mixture density.The United States Patent (USP) No.5,548,125 of Sandbank et al. teaches a kind of comprising soft Property polymer clothes product, the polymer contains the tungsten of relatively smaller volume percentage, for obtaining radiation shield. The United States Patent (USP) No.5,237,930 of Belanger et al. is disclosed containing copper powder and the usually thermoplastic of nylon material Dummy bomb.The JP 63-273664 A of Epson Corporation disclose it is a kind of containing metal silicate fiber, close knit crystalline substance The polyamide of palpus and other materials, as the composite material containing metal.Finally, the United States Patent (USP) No.6 of Bray et al., 048,379 With 6,517,774 trials for disclosing production tungsten polymer composites.It which disclose and polymer and particle diameter are less than 10 The tungsten powder of micron and the second optional bimodal polymers or metallic fiber are combined as composite material, high density material is made Material.These materials of the prior art obtain the compound state of filled polymer, and the filled polymer may have useful close Degree but do not show to allow to extrude, be molded and the viscoplasticity of other useful hot forming production technologies.

Although having carried out substantial amounts of work on composite material, not yet obtain density and be much larger than 10g/cm³Metal Composite material, its Midst density are to show that the single of composite property is measured.The density for increasing these materials will be to composite material It is middle to introduce unique mechanical performance, when in use, obtaining the performance being not present in compared with low-density composite.Need that there is height Density, hypotoxicity and the material in terms of electro magnetic performance, ductility, injection moulding ability and viscoplasticity with improvement performance.

The content of the invention

The present invention relates to a kind of with improved hot property and viscoplasticity or property is manufactured relative to prior art material Metal polymer composite.By selecting metal particle diameter distribution, polymer and processing conditions, material of the invention is multiple by making The excluded volume of polymer-filled minimizes and obtains improved density or other performance and obtain useful viscoelastic in condensation material Property.Gained composite material is in density, the toxicity reduced, improved ductility, improved toughness, improved viscoplasticity (as drawn Stretch modulus, storage modulus, elastic-plastic deformation etc.), electro magnetic performance and machine molding aspect of performance it is compound better than the prior art Material.We have found that density and the serviceability for being true composite material in this technology with the polymer viscoelastic that elongation is weighed Can be with useful Prediction Parameters.When producing useful enhancing performance, the accumulation and particle or mixing of selected particle diameter and distribution Metallic particles the performance that will be enhanced of selection.The density so obtained can be used as the prediction of other useful properties enhancing because Element.The use of the also composite material comprising interface modifier shows improved material property and utilizes with improved performance as extended Rate and other characteristics.Preferable composite material can be with one or more of polymer and one kind with given molecular weight distribution Or more metallic particles of the kind with given distribution combine to obtain the composite material of uniqueness.The material density, reduce Toxicity, improved ductility, improved toughness, improved viscoplasticity and machine molding aspect of performance can be answered better than the prior art Condensation material.We, which have been prepared for true composite material, can simultaneously obtain viscoplasticity.We improve particle by using interface modifier And the combination of polymer and be prepared for composite material.We have found that the composite material of the present invention can pass through carefully blending group Compound and density, mechanical performance, hot property or the electro magnetic performance for obtaining design level.New viscoelastic property can be used for the material A variety of purposes not performed by composite material and easy to manufacture is provided and it is shaped to the material of useful shape.The prior art is filled out Fill material and do not have these characteristics, will performance brittleness and mechanical damage when being pressurized.

In one embodiment of the invention, selected metallic particles of the selection with specified particle diameter and particle diameter distribution and tool There is the polymer that certain molecular weight is distributed to form improved composite material.The particle can have the circularity limited, it promotes most Big property development.In the system, the composite material of metallic particles and fluoropolymer realizes the performance.

Pigment of the high density material containing interface modification of the present invention or other components for improving material visual appearance.It is mixed Metallic particles, bimetallic (such as WC) or the alloying metal composite material of conjunction can be used for adjusting the performance for special-purpose.This A little performances include but not limited to density, hot property such as thermal conductivity, magnetic property, electrical property such as electric conductivity, color etc..These materials and The combination of material can be used as solid-state electrochemistry structure (such as battery) and semiconductor structure.The metal polymerization of preferable higher density Thing material can be also combined to obtain the composite wood of uniqueness with one or more of polymer and one or more of metallic particles Material.Second metal can be combined with high desnity metal.Composite material can include a variety of different combinations of metal and polymer.Metal Metallic particles of the particle containing two kinds of different metals, every kind of metal all have relatively high density.In another embodiment, Metallic particles can include high desnity metal particle and the second metal.Other useful metals of the disclosure are related in the composite Itself cannot obtain the density more than 10 can still provide the metal of useful properties for composite material on the whole.The characteristic can Physical property, acoustic shielding including electrical property, magnetic property including thermal conductivity etc..The bimetallic example includes but not limited to Iron, copper, nickel, cobalt, bismuth, tin, cadmium and zinc.It is final to be adapted to that the material of the present invention allows design engineer to possess adjustment composite material The flexibility of purposes, and unless needed for avoiding using poisonous or radioactive material.Lead or depleted uranium in its typical case not Need again, because the densified composite of the present invention can be used.Need to carry out toxicity or radiation level some adjustment its During it is applied, composite material of the invention can be used successfully in a manner of being designed to performance needed for material.

In short, using the technology of the present invention, metal polymer composite of the invention can provide the polymer of enhancing Composite property.A kind of important material is more than 10g/cm comprising density³Or more, normally about 5 arrive 21g/cm³, about 5 arrive 18g/cm³, more than 11.7g/cm³, more than 12.5g/cm³Or more than 16.0g/cm³Composite material.The composite material includes High desnity metal particle, polymer and optional interfacial modifier material.The composition of the present invention can also contain content at least about Other additives of 0.01-5 weight % such as sight indicator, fluorescent marker, dyestuff or pigment.The composite material bag of the present invention Metal (metal of 47-90 volumes %), the polymer of 0.5-15 weight % containing about 75-99.9 weight % in the composite (polymer of 10-53 volumes %).In the disclosure, we rely on density as a weight that can be adjusted in the composite Characteristic is wanted, but other useful properties can also be designed into composite material.

The metal polymer composite that density improves can be prepared in the following manner：Formed composite material, wherein with The highest possible accumulation of grain or tap density obtain metallic particles and polymer phase only fully takes up the minimum of the particle substantially Excluded volume.Using metallic particles, the accumulation particle and by the particle and enough combination of polymers just so that only The excluded volume of particle is filled, so as to optimize the high density of composite material.Selection metal absolute density is greater than about 5, leads to Often greater than 16g/cm³Metal, it is used to form composite material and puies forward highdensity combination of polymers with selection.Due to metal Grain and the increase of polymers compositions density, therefore composite density increases.Final composite density is largely by multiple The deposition efficiency of metallic particles and the non-duty gap with high density polymer material filling dense packing particle in condensation material Associated efficiency controls.We have found that the deposition efficiency and charging efficiency can be by carefully selecting grain shape, particle diameter and grain Footpath, which is distributed, to be improved.The particle should be greater than 10 microns, and (it is micro- less than 10 that particle diameter is greater than about 10 microns of particles for referring to fraction Rice, in fact, less than 10 weight %, being typically less than the particle of 5 weight % less than 10 microns).The particle diameter distribution of metal should be wide, Generally include about 10 to 1000 microns of particle.Distribution of particles should contain about 10 to 70 microns of at least some (at least 5 weight %'s) Particle, the particle should also contain the particle that at least some (at least 5 weight %) are more than 70, about 70 to 250 microns, optionally described The particle that grain can contain about 250 to 500 microns of (at least 5 weight %) can simultaneously contain some particles in 500+ micrometer ranges.Should Distribution can be normal state, Gauss, lognormal or asymmetric normal distribution, but must include required particle size range.True composite wood Material by carefully process combination polymer and polymer beads up to performance be developed and density reach certain level and Obtain, show using the property development and high density for promoting the interface modifier that composite material is formed to cause enhancing.

Composite material is more than simple mixtures.Composite material is defined as two or more materials and forms hundred with various Divide the composition than mutually adulterating, wherein each component keeps its basic original performance.The controlled combination of independent material is better than The performance of its component.In simple mixtures, mixing material is almost without interaction and almost without performance enhancement.Selection One of material is to improve rigidity, intensity or density.Atom and molecule can pass through a large amount of mechanism and other atoms or molecule bonding.This The key of sample can occur between the electron cloud of atom or molecular surface, including molecule-molecule interaction, atom-molecule phase interaction Interacted with atom-atom.Each bonding mechanism is related to characteristic force and size between atom center, or even in molecule It is also such in interaction.The importance of the bonding force is intensity, bond strength with distance and direction change.The bonding In main power include ionic bond, covalent bond and Van der Waals (VDW) type bonding.Ionic radius and ionic bond occur in ionic Material such as Na⁺Cl^-、Li⁺F^-In.This kind of ionic species form ionic bond between atom center.This generic key be it is firm, usually Substantially greater than 100KJ/mol, often greater than 250KJ/mol.In addition, the interatomic distance of ionic radius tends to very little and is aboutCovalent bond forms direct covalent bonds by the overlapping generation of the electron cloud around atom between atom center.Covalent bond Intensity is quite big, substantially suitable with ionic bond and tend to the interatomic distance with somewhat smaller.

Polytype Van der Waals force is different from covalent bond and ionic bond.These Van der Waals forces tend to as molecular separating force, Rather than the power between atom center.Van der Waals force is generally divided into the power of three types, including dipole-dipole force, dispersion force and Hydrogen bond.Dipole-dipole force is due to that the quantity of electric charge on molecule or distribution temporarily or permanently change a kind of caused Van der Waals force.

Chemical force and interaction are summarized

Interaction type	Intensity	Key characteristic	Intensity proportional in
				Covalent bond	It is very strong	Longer scope	r^-1
Ionic bond	It is very strong	Longer scope	r^-1
				Ion-dipole	By force	Short scope	r^-2
VDW^aDipole-dipole	It is medium strong	Short scope	r^-3
				VDW^aIon-induced dipole	It is weak	Very short scope	r^-4
VDW^aDipole-induced dipole	It is very weak	Extremely short scope	r^-6
				VDW^aLondon dispersion force	It is very weak^b	Extremely short scope	r^-6

^aVan der Waals is abbreviated as " VDW ".

^bSince VDW London forces increase with size increase and molecular dimension is not limited, therefore these power can become suitable Greatly.But in general they are very weak.

Dipole structure is produced by the separation of charge on molecule, produces positive terminal in whole or in part and in whole or in part negative electricity Opposite end.The power is as caused by the electrostatic interaction between the negative electricity of molecule and positive electricity region.Hydrogen bond is hydrogen atom and molecule In electronegativity region between dipole-dipole interaction, the electronegativity region generally includes oxygen, fluorine, nitrogen or other phases To the position of electronegativity (relative to H).These atoms obtain the dipole-dipole interaction caused with positively charged hydrogen atom Dipole negative electrical charge.Dispersion force is the Van der Waals force being present between substantially nonpolar uncharged molecule.Although the power occurs In nonpolar molecule, but the power is due to caused by intramolecular electron motion.Due to the quick movement in electron cloud, When electron motion causes the temporary transient change in molecular polarization, although nonpolar molecule obtains small significant instantaneous charge. These small charge fluctuations cause the dispersive part of Van der Waals force.

The characteristic fluctuated due to dipole or molecular polarization so that it is smaller that such VDW power tends to bond strength, is usually 50KJ/mol or following.In addition, the scope that the power becomes attraction is also substantially greater than ionic bond or covalent bond, and tend to It is about

In the Van der Waals composite material of the present invention, we have found that the different-grain diameter of metallic particles, metal component, particle The improved unique combination of interaction between polymer, causes to produce unique Van der Waals key.Van der Waals force produces Between metallic atom/crystal in particle, and pass through the particle diameter in metal/polymer composite material, polymer and interface modification The combination of agent and produce.Past, be characterized as the material of " composite material " only include be filled between granular filler almost without Or the polymer of the particle without Van der Waals interaction.In the present invention, selected particle diameter distribution and interface modification is poly- Interaction between compound enables particle to obtain the intermolecular distance for producing substantial Van der Waals bond strength.Almost do not have There is viscoelastic prior art material to there is no true composite structure.This, which guides us to derive in the prior art, does not have Obtain the intermolecular distance.In described above, can using term " molecule " to refer to metallic particles, comprising metallic crystal or The particle of amorphous metal aggregation, other molecules or atomic unit or the subunit of metal or metal mixture.In this hair In bright composite material, Van der Waals force occurs working as " molecule " using crystal or other metallic atom aggregate forms Between metallic atom set.The composite material of the present invention is characterized in that composite material with intermolecular between metallic particles Power, in the range of Van der Waals intensity, i.e., about 5 are the molecular separating force to about 30KJ/mol and key sizeThis hair Bright composite material includes metallic particles and polymer, wherein the metallic particles has certain particle size range so that about extremely The particle of few 5 weight % is about 10-70 microns and the particle of about at least 5 weight % is about 70-250 microns, in composite material Adjacent particle molecule between have less than about 4kJ/mol Van der Waals dispersion bond strength andKey size, or Person is less than about the intensity peace treaty of 2kJ/molVan der Waals key size.

In the composite, the strength and stiffness of reinforcing agent are usually more much higher than matrix, and its good performance is assigned Composite material.Matrix contains reinforcing agent with orderly high-density mode.Because reinforcing agent is typically discontinuous, therefore matrix is also Help to shift the load between reinforcing agent.Processing can help to mix and fill metal reinforcing agents.In order to help to mix, interface changes Property agent can help to overcome the power for preventing matrix from forming substantially continuous composite material phase.The performance of composite material is by by using son Fining-off is produced with obtained combine closely is manufactured.It is considered that interface modifier be on particle provide external skin with Promote the organic material combined closely of polymer and particle.Minimal amount of modifying agent, including about 0.005-3 weight % can be used Or about 0.02-2 weight %.

For this disclosure, term " metal " is related to oxidation state metal, and the oxidation state is about 0, at most 25 weight % or About 0.001-10 weight % is as oxide or metal or nonmetallic inclusion, not with ion, covalently or chelating (coordination) agent knot Close.For the present invention, term " particle " is often referred to be made the material of product, what the particle diameter of the product was more than 10 microns and had Particle diameter distribution includes at least some 10-100 microns and 100-4000 microns of particle.In stacking states, which has about The excluded volume of 5-53 volumes %.In the present invention, in the different chemically and physically metal blends of characteristic, particle can wrap Containing two kinds, three or more sources of particles.

In general, the composite material of the present invention is manufactured using melt-processed, melt-processed can also be utilized and be used for product Shaping.In general, in the manufacture of high density material of the present invention, will about 40-96 volumes %, usually from 50-95 volumes % or 80-95 The metallic particles of volume % is under warm and temperature conditionss with about 4-60 volumes %, usually from 5-50 volume % or 5-20 volumes %'s Typical thermoplastic polymers combination of materials, processing is until the density that material obtains is about 5-21g/cm³Or about 5-18g/cm³, Chang great In 10g/cm³、11g/cm³, preferably greater than 12g/cm³, more preferably greater than 16g/cm³, show that true composite material is formed.Typically Elongation is at least 5%, at least about 10% and usually from 5-250%.Alternatively, in the manufacture of material, metal or thermoplastic Property polymer can be blended with interface modifier, the material melt-processable of the subsequent modification is into the material.Once material obtains Enough density, so that it may material is extruded into product with conventional machining techniques or is extruded into pellet, fragment, disk or other is easy to The raw material of the material forms of processing.When manufacturing useful product using the composite material of the present invention, can usually extrude The composite material obtained in right amount is heated and pressurizeed in equipment, is then formed as having in suitable physical configuration appropriate Measure the suitable shape of material., can be by pigment in composite material manufacture or manufacture course of products in suitable product design Or other coloring materials are added in process equipment.One advantage of the material is that inorganic dyestuff or face can be processed at the same time Material, so as to obtain to carry out coated outside or coat to be achieved with attractive or decorative appearance material.Pigment can wrap Include in blend polymer, be evenly distributed in whole material and can obtain fragmentation, scratch or it will not being lost The surface of decorative appearance.A kind of especially important pigment includes titanium dioxide (TiO₂).The material has no toxicity, is brilliant white Particle, can easily combine with metallic particles and/or polymer composites, to increase the density of composite material and be final multiple Condensation material provides white color.

It has been found that two kinds, the blend of the metals of three or more particle forms can be from polymer composites Blending metal in structure obtains important composite property.For example, tungsten compound or other high desnity metal particles can be with Radiating including low α, β or γ particulate forms, desired low cell toxicant are provided for metastable nontoxic tungsten material Property, the second metal blending of additional properties including outward appearance change or other advantageous properties.One of double metallic composite material is excellent Point can produce the ratio of density that be adapted to for specific final use and obtain by carefully selecting.For example, can be with such as fluorine Polymer or fluoropolymer production have 11g/cm³To 12.2g/cm³Solid density tantalum/composite tungsten material.Alternatively, For other application, can be produced with fluoropolymer can have about 12g/cm³To about 13.2g/cm³The iridium composite tungsten material of density. Various such composite materials can have unique or special performance.The processing method and material of these composite materials have uniqueness Ability and performance so that the composite material is used as not utilizing the method for the present invention to make due to fusing point and other processing difficulties Into the alloy composite materials of two kinds of different metals of alloy.

Brief description of the drawings

Fig. 1 is mechanograph or extruded product made of material of the present invention.The figure is available described herein various One example of structure made from method.Stent is soft by having for the metal polymer composite acquisition practicality of the present invention One example of the product of property structure.

Fig. 2A and 2B is the cross section of the extruded product of the present invention.

Fig. 3 A and 3B are two kinds of forms of the fishhook of the snap on system or molding fishing pendant that include composite material of the present invention.

Fig. 4 A and 4B be the present invention automobile or truck inflation tire wheel balancing block two kinds of forms.

Fig. 5-11 provides the viscoplasticity of the display present invention and the technology forms the number of the adaptability of property needed for material According to.

Figure 12-20 displays present invention compared with previous Metallic-filled polymer composition and polymer itself is unique to glue Elasticity.

Figure 21 and 22 explains the uniqueness of the tungsten of the display present invention and the stress-strain diagram of the performance of stainless steel composite material Property.

Figure 23 and 24 is the magnification region of Figure 22.

Figure 25 shows the stress-strain diagram of THV fluoropolymers.

Figure 26 and 27 shows that the filled polymer non-composite material of the prior art is brittle and when applying minimum stress Damage, and the true composite material of the present invention has the useful mechanical performance to have a wide reach.

Figure 29 to 30 shows that the global density of a variety of composite materials of the present invention of the component containing different metal and volume filling are close Degree.

Embodiment

There is enhancing or the improvement of improved viscoplasticity and hot property relative to prior art material the present invention relates to a kind of Metal polymer composite.Single metal and the metallic composite of mixing can be made to be adapted to new capability, including density, face Color, magnetism, thermal conductivity, electric conductivity and other physical properties.Further include the operation instruction material of the composite material of interface modifier The improvement and the improvement of performance that performance utilizes.Preferable composite material can be with the one or more with given molecular weight distribution Polymer and one or more of metallic particles with given distribution combine and obtain the composite material of uniqueness.The present invention relates to A kind of composite material, it is characterised in that there is density and ductility better than lead but without lead and other high density materials Intrinsic toxicity.The material can be used for needing in high density, ductility, toughness, formability and viscoelastic application.The present invention High density material is provided in particular in, which includes high desnity metal particle such as tungsten, polymer phase and optional interface Modifying agent, the interface modifier allow polymer to interact with metallic particles to be formed with required characteristic and degree of performance Composite material and reach maximum potential density.The material obtain including density, storage modulus, color, magnetism, thermal conductivity, Exceed the physical property of prior art material in terms of electric conductivity and other physical property improvement, and unless need in a particular application Will, otherwise without lead or the toxicity or residual radiation feature of the difference of depleted uranium.The material of the present invention allows design engineer to possess Adjustment composite material is with the flexibility of suitable final use and avoids using poisonous or radioactive material, unless needed for.In its allusion quotation Lead or depleted uranium are no longer needed in type application.

The composite material combination metallic particles and polymeric material of the present invention, the metallic particles are stayed in maximum tap density Go out excluded volume, the polymeric material occupies the excluded volume substantially, but no longer occupies more volumes to be answered The density of the maximum possible of condensation material composition.Tap density (ASTM B527-93) be related to material stacking obtain it is how well.Accumulation Influence excluded volume and the volume fraction included in density calculating.A variety of metallic particles with appropriate size and distribution Use.The fact that the metallic particles diameter that the important parameter of metallic particles distribution includes no more than 5 weight % is less than 10 microns.This Outside, have that considerable fraction of particle falls in 10-100 micrometer ranges, considerable fraction of particle falls in metallic particles distribution In 100-250 micrometer ranges and considerable fraction of particle falls in 100-500 micrometer ranges." significant fraction " refer to The particle of few 10 weight %.The distribution can be normal distribution, Gaussian Profile, logarithm normal distribution or asymmetric normal distribution, but It must include required particle size range.

The final densities of metal are at least 11g/cm³, preferably greater than 13g/cm³, more preferably greater than 16g/cm³, polymer Density is at least 0.94g/cm³, but density is more than 1-1.4g/cm³, preferably greater than 1.6g/cm³Polymer for increase density And to obtain useful polymer composites useful.The tensile strength of composite material is 0.2-60MPa, and storage modulus (G ') is About 1380 to about 14000MPa, preferably from about 3450 arrive about 6000MPa, and stretch modulus is at least 0.2-200MPa.The present invention's answers One key character of condensation material is that there are elastic-plastic deformation and its Poisson's ratio.The composite material display elasticity of the present invention Plastic deformation.Under the stress for causing composite material to extend, the structure is deformed up to reaching capacity with elastic model, Zhi Houjie Structure is with plasticity mode deformation until reaching its limit and structural failure.The performance is expressed as elongation at break, and wherein material is being answered Under power at least 5% or at least 10% is extended before reaching elastic limit and being broken under continuous stress.The pool of preferable material Pine is than typically smaller than 0.5, preferably from about 0.1 to about 0.5.

The feature of the particle of currently preferred regular substantially spherical can by the circularity and its aspect ratio of particle come Limit.The aspect ratio of particle should be less than 1: 3, often less than 1: 1.5 and should reflect almost circular section or spheric granules. Circularity, circularity or the roughness of particle can be measured by the micro- detection of particle, wherein automatic or manual can be calculated Roughness metric.In such measurement, the girth of the representative Sexual behavior mode of particle is selected, while measures particle cross section Area.The circularity of particle calculates according to the following formula：

Circularity=(girth)²/ area.

The circularity feature of preferable spheric granules is about 12.6.The circularity feature is less than about 20, is often about 14-20 Or the dimensionless group of 13-18.

Metallic particles in composite material for use in the present invention includes tungsten, uranium, osmium, iridium, platinum, rhenium, gold, neptunium, plutonium and tantalum, And the second metal such as iron, copper, nickel, cobalt, tin, bismuth and zinc can be contained.Can be by non-poison or on-radiation material although an advantage is Material is used as needing substitute at lead and depleted uranium, but can also be used when material not adversely affects expected purposes lead and Uranium.Another advantage is that two or more can be utilized, which to be formed naturally the metal material of alloy, produces bimetallic Or more metallic composite.Multiple performance, material can be adjusted by carefully selecting combination and the polymer of metal or metal Toxicity and radioactivity can design on demand into material.These materials are used not as big metallic particles, and usually as small Metallic particles uses, and is frequently referred to metallic particles.This kind of particle has relatively small aspect ratio, and aspect ratio is generally less than about 1: 3.It is long Ratio of the width than being normally defined the full-size of particle and the minimum dimension of particle.In general, spheric granules is preferable, but enough Bulk density can by compact texture relatively uniform particle obtain.

The composite material combination metallic particles and polymeric material of the present invention, the metallic particles are stayed in maximum tap density Go out excluded volume, the polymeric material occupies the excluded volume substantially, but it is compound to obtain no longer to occupy more volumes The density of the maximum possible of material compositions.

A variety of high desnity metals can be used.The atomic weight of tungsten (W) is 183.84, and atomic number 74, belongs to VIB (6) Race.Naturally occurring isotope is 180 (0.135%), 182 (26.4%), 183 (14.4%), 184 (30.6%), 186 (28.4%), induced radioisotope 173-179,181,185,187-189.Tungsten was sent out in 1781 by C.W.Scheele Now and in 1783 by J.J. and F.de Elhuyar separate.As one of rare metal, it accounts for about 1.5ppm in the earth's crust.It is main The ore wanted is wolframite [(Fe, Mn) WO₄] and scheelite [(CaWO₄)], be primarily present in China, Malaya, Mexico, Ah Lars adds, South America and Portugal.WO of the scheelite containing 0.4-1.0% of U.S.'s exploitation₃.The description of separation process is shown in K.C.Li, C.Y.Wang, Tungsten, A.C.S.Monograph Series no.94 (Reinhold, New York, 3rd Ed., 1955) the 113-269 pages；G.D.Rieck, Tungsten and Its Compounds (Pergamon Press, New York, 1967) page 154.Summary：Parish, Advan.Inorg.Chem.Radiochem.9,315-354 (1966)； Rollinson, " Chromium, Molybdenum and Tungsten ", Comprehensive Inorganic Volume 3, J.C.Bailar, Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 623- of Chemistry 624th, 742-769 pages.Tungsten is body-centered cubic structure for steel grey to tin white non-ferrous metal, crystalline form.Its density is d₄ ²⁰ 18.7- 19.3；Its hardness is 6.5-7.5, and fusing point is 3410 DEG C, and boiling point is 5900 DEG C, and (20 DEG C) of specific heat is 0.032cal/g/ DEG C, fusing Heat is 44cal/g, and heat of evaporation 1150cal/g, (20 DEG C) of resistivity is 5.5 μ Ω cm.Tungsten is stablized in dry air under room temperature But trioxide is formed under red heat, is dioxide not by aqueous corrosion but by steam oxidation.Granular tungsten is under suitable condition Can spontaneous combustion can simultaneously be slowly dissolved in the presence of air in molten potassium hydroxide or sodium carbonate；Dissolve in the molten of NaOH and nitrate Melt in mixture.Tungsten is corroded by fluorine at room temperature；By chlorine corrosion at 250-300 DEG C, there is no obtaining hexachloride during air, There are obtain trioxide and oxychloride during air.In short, fusing point is 3410 DEG C, and boiling point is 5900 DEG C, density d₄ ²⁰ 18.7-19.3。

The atomic weight of uranium (U) is 238.0289 (being characterized as naturally occurring isotopic mixture), and atomic number 92, does not have There is stable nuclide.Naturally occurring isotope is 238 (99.275%), 235 (0.718%), 234 (0.005%)；Artificial radioactivity Property isotope is 226-233,236,237,239,240.Uranium accounts for about 2.1ppm in the earth's crust.The main uranium ore for having commercial significance is Carnotite, pitch blende, chalcolite (tobernite) and autunite.Commercially important mineral reserve are positioned at Canadian Elliot Lake-Blind River basins, the Rand goldfields in South Africa, the Colorado in the U.S. and the Utah State, Australia And France.See M.H.Klaproth, Chem.Ann.II, 387 (1789) from the discovery of pitch blende.The preparation of the metal is shown in E.Peligot, C.R.Acad.Sci 12,735 (1841) and Idem, Ann.Chim.Phys.5,5 (1842).Pure uranium metal Preparation flow and details are shown in Chem.Eng.62, No.10,113 (1955)；The United States Patent (USP) 2,852,364 of Spedding etc. (authorizing U.S.A.E.C. within 1958).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 of Uranium (Elsevier, New York, 1969) pages 2550；Numerical digit Author is in Handb.Exp.Pharmakol, 36,3-306 (1973)；" The Actinides ", Comprehensive Volume 5, J.C.Bailar, Jr., et al., Eds. of Inorganic Chemistry (Pergamon Press, Oxford, 1973)passim；F.Weigel, Kirk-Othmer Encyclopedia of Chemical Technology volumes 23 The 502-547 pages of (Wiley-Interscience, New York, 3rd ed., 1983)；Idem, The Chemistry of The Actinide Elements volumes 1, J.J.Katz et al., Eds. (Chapman and Hall, New York 1986) the 169-442 pages；J.C.Spirlet et al., Adv.Inorg.Chem.31,1-40 (1987).On toxicology and The summary of health effect is shown in Toxicological Profile for Uranium (PB91-180471,1990) pages 205.Uranium For silvery white, glossiness radioactive metal, it quickly tarnishes to form black in atmosphere with ductility and toughness Oxide skin(coating).Heat of evaporation is 446.7kJ/mol；Heat of fusion is 19.7kJ/mol；The heat of sublimation is 487.9kJ/mol.Granular uranium gold Belong to and some uranium compounds spontaneous combustion and can be quickly dissolved into HCl/water solution in air or oxygen.Non-oxidizing acid such as sulfuric acid, Phosphoric acid and hydrofluoric acid are only very slowly reacted with uranium；Nitric acid is with moderate rate dissolved uranium；Dissolving of the granular uranium in nitric acid can Near-by explosion intensity.Uranium metal is to alkali inertia.In short, fusing point is 1132.8 ± 0.8 DEG C, density 19.07；d 18.11；d 18.06.

The atomic weight of osmium (O) is 190.23, and atomic number 76, belongs to VIII (8) race.Naturally occurring isotope is 184 (0.02%), 186 (1.6%), 187 (1.6%), 188 (13.3%), 189 (16.1%), 190 (26.4%), 192 (41.0%).Induced radioisotope is 181-183,185,191,193-195.Osmium accounted in the earth's crust about 0.001ppm and Found in osirita ore and all platinum ores.Tennant was found that osmium in 1804.Berzelius et al. are shown in preparation, (Mellor references), A Comprehensive Treatise on Inorganic and Theoretical Chemistry 15,6887 (1936).Summary：Gilchrist, Chem.Rev.32,277-372 (1943)；Beamish et al., Rare The 291-328 pages of Metals Handbook, C.A.Hampel, Ed. (Reinhold New York, 1956)；Griffith, Quart.Rev.19,254-273 (1965)；Idem, The Chemistry of the Rarer Platinum Metals The 1-125 pages of (John Wiley, New York, 1967)；Livingstone, Comprehensive Inorganic Chemistry, volume 3, J.C.Bailar, Jr.et al.Eds. (Pergamon Press, Oxford, 1973) 1163- 1189th, 1209-1233 pages.Osmium is blue and white, glossiness metal, has closely packed hexagonal structure.Density is d₄ ²⁰ 22.61, it is being considered as the highest element of density for a long time.Its density of X-ray as shown by data is slightly below iridium, and fusing point is About 2700 DEG C, boiling point is about 5500 DEG C, density d₄ ²⁰22.61, (0 DEG C) of specific heat is 0.0309cal/g/ DEG C, hardness 7.0 (Mohs' hardness).Osmium is stablized in cold air, and granular osmium even also can slowly be oxidized to tetroxide by air at normal temperatures.Osmium By dry chlorine corrosion under being heated more than 100 DEG C by fluorine burn into, but do not corroded by bromine or iodine.Osmium is aoxidized by chloroazotic acid burn into Property acid through a long time is corroded, but hardly by HCl, H₂SO₄Influence.Osmium burns in phosphorous vapor to be formed phosphide, is steamed in sulphur Burning forms sulfide in gas.Alkali metal sulphuric acid hydrogen salt, potassium hydroxide and the oxidant 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, density d₄ ²⁰ 22.61。

The atomic weight of iridium (Ir) is 192.217, atomic number 77.Naturally occurring isotope for 191 (38.5%), 193 (61.5%), induced radioisotope 182-191,194-198.It accounts for about 0.001ppm in the earth's crust.Iridium is What Tennant had found.It is present in nature with metallic state, is existed usually as with the native alloy of osmium (iridosmine), hair Now alloy is formed with platina (platinum ore) or with rusty gold on a small quantity.Deville is shown in by the recycling and purifying of iridosmine, Debray, Ann.Chim.Phys.61,84 (1861)；Wichers is shown in by the recycling and purifying of platinum ore, J.Res.Nat.Bur.Stand.10,819 (1933).Summary on the preparation of iridium and other platinum metal, property and chemistry See：Gilchrist, Chem.Rev.32,277-372 (1943)；W.P.Griffith, the Chemistry of the Rare Platinum Metals (John Wiley, New York, 1967) 1-41,227-312 page；Livingstone, Comprehensive Inorganic Chemistry volumes 3, J.C.Bailar Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 1163-1189,1254-1274 page.Iridium is silvery white, stone metal, is stood with the center of area Prismatic crystal lattice, fusing point are 2450 DEG C, and boiling point is about 4500 DEG C, density d₄ ²⁰22.65, specific heat is 0.0307cal/g/ DEG C, Mohs Hardness is 6.5, is that proportion is highest in all elements.Pure iridium is not included the acid corrosion including chloroazotic acid, and what is be only melted is (non-oxygen The property changed) alkali slight erosion.It is aoxidized in heating condition lower surface in atmosphere, in red heat by fluorine and chlorine corrosion, during melting Corroded by the mixture of potassium sulfate or potassium hydroxide and potassium nitrate, corroded by lead, zinc or tin.Granulated metal is in red heat by air Or dioxygen oxidation is into dioxide, IrO₂, but during further heating, dioxide resolves into its constituent.In short, iridium Fusing point be 2450 DEG C, boiling point is about 4500 DEG C, density d₄ ²⁰ 22.65。

The atomic weight of platinum (Pt) is 195.078, and atomic number 78, belongs to VIII (10) race.Naturally occurring isotope For 190 (0.01%), 192 (0.8%), 194 (32.9%), 195 (33.8%), 196 (25.2%), 198 (7.2%), 190 are It is radioactive：T_1/2For 6.9 × 10¹¹Year.Induced radioisotope is 173-189,191,193,197,199-201.Platinum is on ground About 0.01ppm is accounted in shell.It is believed that Pliny once refers to it with title " alutiae ", in South America with " platina del Pinto " is well known and uses.Platinum is Ulloa reports in 1735, and Europe is taken to and in 1741 by Watson by Wood Description.Its with the alloy with one or more of platinum group members (iridium, osmium, palladium, rhodium and ruthenium) be naturally occurring in gravel and In sand.Wichers et al, Trans.Amer.Inst.Min, Met.Eng.76,602 (1928) are shown in preparation.On platinum and its The summary of the preparation of its platinum metal, property 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 pages；Livingstone, Comprehensive Inorganic Chemistry, volume 3, J.C.Bailar, Jr.et al., Eds. (Pergamon press, Oxford, 1973) 1163-1189,1330-1370 page；F.R.Harley, The Chemistry of Platinum and Palladium with Particular Reference to Complexes of the Elements (Halsted Press, New York, 1973).Platinum be silver gray, it is glossy, can prolong Exhibition, the metal of flexible, have face-centred cubic structure, are prepared in the form of black particle (platinum black) and cavernous body (platinum is continuous).Platinum Fusing point is 1773.5 ± 1 DEG C；Roeser et al., Nat.Bur.Stand.J.Res.6,1119 (1931))；Boiling point is about 3827 DEG C, density d₄ ²⁰(21.447 calculated value)；Brinell hardness is 55；Specific heat at 0 DEG C is 0.0314cal/g；Resistivity (20 DEG C) are 10.6 μ Ω cm；It is not tarnished in air, hydrogen is absorbed during red heat and is retained securely at room temperature It；Gas is discharged during vacuum red heat；Contain carbon monoxide, carbon dioxide and nitrogen；It is heated in atmosphere obvious at 1500 DEG C Volatilization.The Metal absorption oxygen of heating is simultaneously discharged while cooling.Platinum influences from water or single inorganic acid, the chloroazotic acid with boiling Reaction forms chloroplatinic acid, and the equally alkaline cyanide also with melting reacts.It is by halogen, fused caustic (soda), alkali Metrate, alkaline peroxide burn into and corroded in the presence of a reducing agent by arsenate and phosphate.In short, platinum Fusing point be 1773.5 ± 1 DEG C；Roeser et al., Nat.Bur.Stand.J.Res.6,1119 (1931), boiling point are about 3827 DEG C, density is 21.447 (calculated values).

The atomic weight of golden (Au) is 196.96655, and atomic number 79, belongs to IB (11) race.Naturally occurring isotope For 197；Transmutation product (mass number) is 177-179,181,183,185-196,198-203.Gold accounts for 0.005 in the earth's crust. Gold is probably the first simple metal that the mankind know., to be naturally occurring in nature, very small amount is present in nearly all for it In rock and seawater.Gold mine includes calaverite (AuTe₂), aurotellurite [(Ag, Au) Te₂], antamokite [(Ag, Au)₂Te]。 The method of exploitation, extraction and refining is shown in Hull, Stent, Modern Chemical Processes, volume 5 (Reinhold, New York, 1958) the 60-71 pages.Prepared by the laboratory from gold plaque to goldc grains sees Block, Inorg.Syn 4,15 (1953). The chemistry for treating the golden medicine of rheumatoid arthritis is shown in D.H.Brown, W.E.Smith, Chem.Soc.Rev.9,217 (1980). Passing through NO₂Purposes in oxidation of organic compounds as catalyst is shown in R.E.Sievers, S.A.Nyarady, J.Am.Chem.Soc.107,3726 (1985).See in the minimum metal of the interface reactivity with gas or liquid B.Hammer, J.K.Norskov, Nature 373,238 (1995).Summary：Gmelin ' s Handb.Anorg.Chem., Gold (the 8th edition) the 62, the 2nd, 3 parts (1954)；Johnson, Davis, " Gold ", Comprehensive Inorganic Chemistry, volume 3, J.C.Bailar Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 129- Page 186；J.G.Cohn, E.W.Stern, Kirk-Othmer Encyclopedia of Chemical Technology the 11st Volume (Wiley Interscience, New York, the 3rd edition, 1980) the 972-995 pages.Gold is yellow soft metal, has the center of area Cubic structure, darkviolet, purple or ruby red particle, fusing point 1064.76 are obtained when being prepared by volatilization or the precipitation method DEG C, boiling point is 2700 DEG C, density 19.3, Mohs' hardness 2.5-3.0, Brinell hardness 18.5.Golden extreme torpescence；From Acid, air or oxygen corrosion；At room temperature by halogen aqueous corrosion surface；Reacted with chloroazotic acid, if containing chloride, bromide Or the halogen that the mixture of iodide can produce new life especially contains then with mixture reaction with many oxidizing mixtures There is the solution reaction of halogen, alkaline cyanide, rhodanate and double cyanide.In short, golden fusing point is 1064.76 DEG C, Boiling point is 2700 DEG C, density 19.3.

The atomic weight of rhenium (Re) is 186.207, and atomic number 75, belongs to VIIB (7) race.Naturally occurring isotope is 185 (37.07%), 187 (62.93%), the latter are radioactive, T_1/2About 10¹¹Year；Induced radioisotope is 177- 184、186、188-192.Rhenium accounts for about 0.001ppm in the earth's crust.It is present in gadolinite, molybdenite, columbite, Rare Earth Mine In some sulfide ores.Rhenium is the discoveries such as Nodack (Naturwiss.13,567,571 (1925)).Rhenium metal passes through height Hurd, Brim, Inorg.Syn1,175 (1939) are shown in the preparation of the reduction of rehenic acid potassium 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 The 347-364 pages of Handbook, C.A.Hampel, Ed. (Reinhold, New York, 1954)；Peacock, Volume 3, J.C.Bailar, Jr.et al., Eds. (Pergamon of Comprehensive Inorganic Chemistry Press, Oxford, 1973) the 905-978 pages；P.M.Treichei, Kirk-Othmer Encyclopedia of Chemical Technology volumes 20 (Wiley-Interscience, New York, the 3rd edition, 1982) the 249-258 pages. Rhenium has Hexagonal close accumulation crystallization, arrives silver gray to be black, density is d 21.02, and fusing point is 3180 DEG C, and boiling point is 5900 DEG C (estimation), (0-20 DEG C) of specific heat are 0.03263cal/g/ DEG C, and (20 DEG C) of ratio resistance is 0.21 × 10^-4Ω/cm, Brinell hardness are 250, evaporation latent heat 152kcal/mol, react with oxidizing acid, nitric acid and strong sulfuric acid response but not with HCl.In short, The fusing point of rhenium is 3180 DEG C, and boiling point is 5900 DEG C (estimations), density 21.02.

The atomic number of neptunium (Np) is 93.It is that the first does not have the artificial transuranic element of stable nuclide.Known same position Plain (mass number) is 227-242.239 (T of isotope_1/22.355 days, alpha decay, relative atomic mass 239.0529) discovery It can be seen that E.McMillan, P.Abelson, Phys.Rev.57,1185 (1940)；237 (T of isotope_1/2 2.14×10⁶Year, the longevity Order longest known isotope, 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.Seaborg is shown in presence of the neptunium in nature, Perlman, ibid.70,1571 (1948).Chemical property is shown in Seaborg, Wahl, ibid.1128.Summary：C.Keller, the Chemistry of the Transactinide Elements (Verlag Chemie, Weinheim, English Ed., 1971) the 253-332 pages；W.W.Schulz, G.E.Benedict, Neptunium-237：Production and Recovery, AEC Critical Review Series (USAEC, Washington D.C.), 1972) page 85； Volume 5, J.C.Bailar, Jr.et al., Eds. (Pergamon of Comprehensive Inorganic Chemistry Press, Oxford, 1973) passim；J.A.Fahey, The Chemistry of the Actinide Elements the 1st Volume, the 443-498 pages of J.J.Katz et al., Eds (Chapman and Hall, New York, 1986)； G.T.Seaborg, Kirk-Othmer Encyclopedia of Chemical Technology (Wiley- of volume 1 Interscience, New York, the 4th edition, 1991) the 412-444 pages.Neptunium is argentine, and the short time is exposed in air When form thin oxide layer.Under high temperature NpO is formed with air reaction₂, with 4174 DEG C of extrapolation boiling point.Neptunium is in the solution Obtain five oxidation state；Most stable of is five valence states.Tetravalent neptunium is easy to be oxidized to hexavalent state by cold permanganate or strong oxidizer； Electroreduction obtains trivalent form in blanket of nitrogen.In short, the fusing point of neptunium is 637 DEG C, and boiling point is 4174 DEG C, density d 20.45；d 19.36.

The atomic number of plutonium (Pu) is 94, the nucleic do not stablized.Known isotope (mass number) is 232-246.Most The known isotope of long-life is²⁴²Pu(T_1/2 3.76×10⁵Year, relative atomic mass 242.0587), 244 (T_1/2 8.26× 10⁷Year, relative atomic mass 244.0642).Commercially useful isotope is²³⁸Pu(T_1/287.74 year, relative atomic mass 238.0496)、²³⁹Pu(T_1/2 2.41×10⁴Year, relative atomic mass 239.0522).Plutonium accounts for 10 in the earth's crust^-22%.Same position Element²³⁸G.T.Seaborg et al., Phys.Rev.69,366,367 (1946) are shown in the discovery of Pu；Isotope²³⁹The discovery of Pu is shown in J.W.Kennedy et al., ibid 70 555 (1946).From pitch blende²³⁹The 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) page 653；C.Keller, The Chemistry of the Transuranium The 333-484 pages of Elements (Verlag Chemie, Weinheim, English Ed., 1971)；Comprehensive Volume 5, J.C.Bailar, Jr.et al., Eds. of Inorganic Chemistry (Pergamon Press, Oxford, 1973)passim；Handb.Exp.Pharmakol 36 307-688(1973)；F.Weigel, Kirk-Othmer Encyclopedia of Chemical Technology volumes 18 (Wiley-Interscience, New York, the 3rd edition, 1982) the 278-301 pages；Plutonium Chemistry, W.T.Carnall, G.R.Choppin, Eds. (Am.Chem.Soc., Washington, D.C., 1983) page 484；F.Weigel etc., The Chemistry of the Actinide Elements volumes 1, J.J.Katz et al., Eds. (Chapman and Hall, New York, 1986) 499-886 pages.Toxicology summary is shown in W.J.Bair, R.C.Thompson, Science 183,715-722 (1974)；Healthy shadow Sound is shown in Toxicological Profile for Plutonium (PB91-180406,1999) pages 206.Plutonium is silvery white coloured gold Belong to, there is highly reactive property.It is easy to aoxidize in dry air and oxygen, and speed is accelerated in the presence of moisture.In short, plutonium Fusing point be 640 ± 2 DEG C, density d²¹19.86；d¹⁹⁰17.70；d²³⁵17.14；d³²⁰15.92；d⁴⁰⁵16.00；d⁴⁹⁰ 16.51。

The atomic weight of tantalum (Ta) is 180.9479, and atomic number 73, belongs to VB (5) race.Naturally occurring isotope is 181 (99.9877%)；180 (0.0123%), T_1/2＞ 10¹²Year；Induced radioisotope is 172-179；182-186.Tantalum Almost always with niobium association, but content does not have niobium to enrich.Tantalum is present in columbite, tantalite ([(Fe, Mn) (Ta, Nb)₂O₆]) and Microlite [(Na, Ca)₂Ta₂O₆(O, OH, F)] in.Tantalum was found in 1802 by Edeberg；Its pure substance is obtained by Bolton first Obtain (Z.Elektrochem.11,45 (1905)).Schoeller, Powell, J.Chem.Soc.119,1927 are shown in preparation (1921).Summary：G.L.Miller, Tantalum and Niobium (Academic Press, New York, 1959) Page 767；Brown, " The Chemistry of Niobium and Tantalum ", Comprehensive Inorganic Volume 3, J.C.Bailar, Jr.et al., Eds. (Pergamon Press, Oxford, 1973) 553-622 of Chemistry Page.Tantalum is grey, stone, extending, toughness metal, it can be easy to pull into filament；Fusing point is 2996 DEG C, boiling point 5429 DEG C, density is d 16.69, and (0 DEG C) of specific heat is 0.036cal/g/ DEG C, resistivity (18 DEG C)：12.4 μ Ω cm, it is not soluble in water, It is very resistant to chemical etching, not by hydrofluoric acid outside other acid corrosions, also do not corroded by aqueous alkali, the alkali being melted is slowly rotten Erosion.It is only reacted with fluorine, chlorine and oxygen under heating, and absorbs the hydrogen of hundreds of times of own vols at high temperature；With nitrogen, carbonization Close.In short, the fusing point of tantalum is 2996 DEG C, and boiling point is 5429 DEG C, density d 16.69.

In many polymeric materials composite material for use in the present invention.For the purpose of the application, polymer this General terms covers thermosetting property and thermoplastic.We have found that polymeric material for use in the present invention includes polycondensation material Material and addition or vinyl polymerization material.Included is polyvinyl and condensation polymer and its polymer alloy.Vinyl Polymer is usually manufactured by the monomer polymerization with ethylenic unsaturation ethylenic group.Condensation polymer is usually utilized and is commonly referred to be Prepared by the polycondensation reaction progressively chemically reacted, wherein making two or more molecule chemical combination, often but necessarily with water or one A little other simply typically separation of volatile material.The polymer can be formed during referred to as polycondensation.It is described poly- The density of compound is at least 0.85g/cm³, but polymer of the density more than 0.96 is useful for the global density for improving product.Take Certainly in metallic particles and final use, density is often to a height of 1.7 or extremely a height of 2g/cm³Or it can be about 1.5-1.95g/cm³。

Polyvinyl includes polyethylene, polypropylene, polybutene, acrylonitrile-butadiene-styrene (ABS) (ABS), polybutene Copolymer, poly- acetyl resin, polyacrylics, include vinyl chloride, the homopolymer of vinylidene chloride or copolymer, carbon fluorine Compound copolymer etc..Condensation polymer includes nylon, phenoxy resin, polyarylether such as polyphenylene oxide, polyphenyl thioether material；Makrolon Material, chlorinated polyether resin, polyethersulfone resin, polyphenylene oxide resin, polysulfone resin, polyimide resin, thermoplastic polyurethane bullet Property body and many other resin materials.

Condensation polymer in composite material for use in the present invention includes polyamide, polyamide-imide polymer, poly- virtue It is sulfone, makrolon, polybutylene terephthalate (PBT), polybutylene naphthalate, polyetherimide, polyether sulfone, poly- to benzene Naphthalate, thermoplastic polyimide, polyphenylene ether blend, polyphenylene sulfide, polysulfones, thermoplastic polyurethane etc..It is preferred that Condensation engineering polymers include makrolon material, polyphenyl ether material and polyester material (including polyethylene terephthalate Ester, polybutylene terephthalate (PBT), polyethylene naphthalate and polybutylene naphthalate material).

Makrolon engineering polymers for high-performance, unbodied engineered thermoplastic materials, its with high impact, thoroughly Lightness, heat resistance and dimensional stability.Makrolon is generally divided into polyester or the carbonic acid with organic hydroxy compounds.It is the most frequently used Makrolon be copolymerized based on the phenol A as hydroxy compounds and carbonic acid.Material usually passes through bisphenol-A and phosgene (O=CCl₂) Reaction prepare.Makrolon can be for example resistance to improve performance by introducing phthalate ester monomers preparation into polymerization extruder It is hot, trifunctional material can also be used in addition to increase melt strength or extrusion-blown modling material.In alloy is manufactured, poly- carbonic acid Ester can often be used as with the component that other commercial polymer are combined as general intermingling material.Makrolon can be with poly- to benzene Naphthalate, acrylonitrile-butadiene-styrene (ABS), maleic anhydride of styrene etc. combine.Preferable alloy includes styrene Copolymer and makrolon.The melt index (MI) of preferable makrolon material should be 0.5-7g/10 minutes, preferably 1-5g/10 points Clock.

In a variety of polycondensation of polyester thing material composite materials for use in the present invention, including polyethylene terephthalate, Polybutylene terephthalate (PBT), polyethylene naphthalate, polybutylene naphthalate etc..Poly terephthalic acid second two Alcohol ester and polybutylene terephthalate (PBT) are high performance condensation polymer material.This kind of polymer usually through glycol (ethylene glycol, 1, 4- butanediols) copolymerization between dimethyl terephthalate (DMT) and prepare.In the polymerization of the material, polyblend is heated to High temperature and occur discharge methanol ester exchange reaction and form engineering plastics.Equally, polyethylene naphthalate and poly- naphthalene two Formic acid butanediol ester material can be prepared by the use of naphthalenedicarboxylic acid as acid source by copolymerization ibid.With terephthalic acid (TPA) ester material phase Than naphthalate thermoplastic has the Tg of higher and the high-temperature stability of higher.But all these polyester materials In composite material for the present invention.This kind of material has the preferred molecular weight characterized by fluidity of molten.Useful polyester Viscosity of the material at 265 DEG C is about 500-2000cP, preferably from about 800-1300cP.

Polyphenyl ether material is engineered thermoplastic materials, within the temperature range of up to 330 DEG C.Polyphenylene oxide has excellent Mechanical performance, dimensional stability and dielectric property.In general, polyphenylene oxide is as the polymer alloy with other polymer or fiber Or blend production and sale.Polyphenylene oxide generally comprises the homopolymer of 2,6- dimethyl -1- phenol.The polymer is commonly referred to as Poly- (oxygen-(2,6- dimethyl-Isosorbide-5-Nitrae-phenylene)).Polyphenylene oxide is often with the alloy or blending with polyamide (being typically nylon 6-6) Thing, the alloy use with polystyrene or HI high impact styrene etc..The preferable melt of polyphenyl ether material that can be used in the present invention Index (ASTM 1238) is typically about 1-20g/10 minutes, preferably from about 5-10g/10 minutes.Melt viscosity at 265 DEG C is about 1000cP。

Another kind of thermoplastic includes styrol copolymer.Term styrol copolymer refers to styrene and the second vinyl Monomer copolymerization obtains polyvinyl.Styrene of this kind of material containing at least 5 moles %, remaining is other for one or more Vinyl monomer.An important kind in these materials is styrene-acrylonitrile (SAN) polymer.SAN polymer is random Amorphous linear copolymers, are produced by styrene, acrylonitrile and optional other monomer copolymerizations.Lotion, suspension and company are used Continuous bulk polymerization techniques.San copolymer has transparent, excellent hot property, good chemical resistance and hardness.These polymerizations Thing is also characterized by its rigidity, dimensional stability and bearing capacity.Olefin-modified SAN (OSA polymeric materials) and acrylic compounds (acrylic) styrene-acrylonitrile (ASA polymeric materials) is well known.These materials are slightly softer than unmodified SAN, be have it is tough Property, opaque two-phase terpolymer, have unexpected improved weatherability.

ASA polymer is random amorphous terpolymer, is produced by bulk copolymerization or by graft copolymerization.In body In copolymerization, acrylic monomer, styrene and acrylonitrile are combined to form mixed embedding terpolymer.In another technology of preparing In, styrene-acrylonitrile oligomer and monomer can be grafted on acrylic elastomer main chain.This kind of material, which has, is used as open air Weather-proof and the product of resistance to UV feature, the product are stablized in outdoor exposure with excellent colour stability retentivity and property Property.These materials can also be blended with a variety of other polymer (including polyvinyl chloride, makrolon, polymethyl methacrylate etc.) Or alloying.A kind of important styrol copolymer includes acrylonitrile-butadiene-styrene (ABS) monomer.These polymer are very General engineered thermoplastic materials, are produced by three kinds of monomer copolymerizations.Each monomer provides for final terpolymer material Important properties.Final material has excellent heat resistance, chemical resistance and case hardness and machinability, rigidity and strong Degree.The polymer is also tough and tensile and impact-resistant.The melt index (MI) of styrene copolymers polymer is about 0.5 to 25, excellent Choosing about 0.5 to 20.

A kind of important engineering polymers in composite material for use in the present invention includes acrylic polymer.Propylene Acids polymers include extensive polymer and copolymer, wherein main monomer component is acrylate or methacrylic acid Ester.These polymer are often provided with hard clear sheet or pellet form.Acrylic monomer usually passes through peroxide, azo The free radical process polymerization that compound or radiation energy trigger.Commercial polymer formula is often provided, wherein various additives are poly- Modifying agent used, a series of particular characteristics are provided for application-specific during conjunction.The pellet prepared for grade polymer application is usual Either with polymerisation in bulk (continuous solution polymerization) then extrusion and be granulated and prepare or continuously polymerize in an extruder and Prepare, unconverted monomer decompression in an extruder removes simultaneously circulation and stress.Acrylics are usually with methyl acrylate, first It is prepared by base methyl acrylate, acrylic acid higher alkyl esters and other copolymerizable vinyl monomers.It is for use in the present invention compound The melt index (MI) of preferable acrylic polymeric material in material is about 0.5-50g/10 minutes, preferably from about 1-30g/10 points Clock.

Polyvinyl includes acrylonitrile；The polymer of alpha-olefin such as ethene, propylene etc.；Chlorinated monomer such as vinyl chloride, Vinylidene chloride, acrylate monomer such as acrylic acid, methyl acrylate, methyl methacrylate, acrylamide, acrylic acid hydroxyl second Ester etc.；Styrene monomer such as styrene, α-methylstyrene, vinyltoluene etc.；Vinylacetate；It is generally easy to other Obtained ethylenically unsaturated monomers composition.

Blend polymer or polymer alloy can be used in the production of the pellet or linear extrudate of the present invention.This kind of conjunction Gold generally comprises two kinds of polymer that can be mixed, its blending forms homogeneous compositions.Science and business in blend polymer field Industry progress already leads to realize not by developing novel polymer material and by forming the blend polymer or alloy that can mix Improved to reach important physical property.The polymer alloy of equilibrium state includes the mixture of two kinds of amorphous polymers, described Two kinds of polymer exists as the single-phase of the close mixing segment of two kinds of macromolecular components.The amorphous polymer that can be mixed once Enough coolings form glass, and blend polymer that is uniform or can mixing has the single glass transition dependent on composition Temperature (Tg).It can not mix or the blend polymer of no-alloyed usually shows two or more with the polymer phase that can not mix Multiple glass transition temperatures.In the simplest situations, the group for the performance that the performance of polymer alloy is possessed by each component Reflect into weighted average.But in general, performance to the dependence of composition in a complex manner with the spy of specific performance, component Property (glassy, rubber-like or hypocrystalline), the thermodynamic state of blend and its molecule and the machine performance that mutually whether is orientated and Change.

Basic demand for being essentially engineering thermoplastic polymeric material is to maintain enough thermoplasticity, such as viscosity and surely It is qualitative, allowing melt and metallic particles to be blended, allowing to form linear extrudate pellet and allowing composition material or pellet to exist In thermoplastic process extrude or be injection moulded with formed with product.Engineering polymers and polymer alloy can be from many productions Bought at business, including Dyneon LLC, B.F.Goodrich, G.E., Dow and duPont.

Polyester polymers are produced by the reaction of binary acid and dihydric alcohol.Include adjacent benzene for the binary acid in production of polyester Dicarboxylic acid anhydride, M-phthalic acid, maleic acid and adipic acid.Phthalic acid provides rigidity, hardness and temperature tolerance；Maleic acid provides Vinyl saturation is to adapt to radically curing；Adipic acid provides flexible and toughness for solidification polymer.Common dihydric alcohol is third Glycol, it reduces crystallization and is inclined to and improves the dissolubility in styrene.Ethylene glycol and diethylene glycol (DEG) reduce crystallization tendency.Binary acid and Dihydric alcohol eliminates water through condensation, is then dissolved in vinyl monomer to suitable viscosity.Vinyl monomer includes styrene, second Alkenyl toluene, p-methylstyrene, methyl methacrylate and diallyl phthalate.Add polymerization initiator such as hydrogen Quinone, tert-butyl catechol or phenothiazine are to extend the storage life of uncured polyester polymers.It is poly- based on phthalic anhydride Compound is referred to as phthalic acid polyester, and the polymer based on M-phthalic acid is referred to as isophthalic polyester.Unsaturation is poly- The viscosity of ester polymer can be adjusted according to application.Low viscosity is good for ensuring in the manufacture of fibre reinforced composites The follow-up high adhesion to following base material of wetability and enhancement layer it is critically important.Wetability difference can cause the significantly damage of mechanical performance Lose.In general, polyester is 200-1, the concentration of styrene of the polymer of 000MPa.s (cP) or other lists with production uncured viscosity Bulk concentration produces.The viscosity of tailor-made polymer thing can be about 20cP to 2,000cP.Unsaturated polyester (UP) polymer was usually by commonly using The radical initiator of oxide material production cures.A variety of peroxide initiators are commercially available and commonly use.Peroxide draws Hair agent is decomposed thermally to form free radical and triggers kind.

Phenol polymer can also be used for the structure member of the manufacture present invention.Phenol polymer generally comprises phenol-aldehyde polymer. This kind of polymer person's character fire resisting, heat-resisting and cost are low.Phenol polymer is usually by being blended phenol and the first less than stoichiometry Aldehyde is prepared.The condensation of these material use acid catalysts produces the thermoplasticity midbody polymer for being known as NOVOLAK.These polymer For the oligomer of phenolic group end-blocking.In the presence of a curing agent and optionally under heating, it is very high that the oligomer is formed by curing molecular weight Thermosetting polymer.Curing agent for novalak is usually aldehyde compound or methylene (- CH₂-) donor.Aldehydes cures Agent includes paraformaldehyde, hexa, formaldehyde, propionic aldehyde, glyoxal and pregnancy ylmethoxy melamine.

The fluoropolymer that can be used in the present invention for the perfluorinate as made from the monomer containing one or more fluorine atoms and The copolymer of partially fluorinated polymer or two or more this kind of monomers.Available for the fluorine in these polymer or copolymer Changing the common instance of monomer includes tetrafluoroethene (TFE), hexafluoropropene (HFP), vinylidene fluoride (VDF), perfluoro alkyl ethylene Base ether such as perfluor-(n-propyl-vinyl) ether (PPVE) or perfluoro methyl vinyl ether (PMVE).Other copolymerizable olefines Monomer (including non-fluorinated monomer) also may be present.

For fluoropolymer, particularly useful material is that (melting temperature is about 100 to arrive to TFE-HFP-VDF terpolymers 260℃；Melt flow index under 265 DEG C and 5kg load is about 1-30g/10 minutes), hexafluoropropene-tetrafluoroethylene-Ethylene (HTE) (melting temperature is about 150 to 280 DEG C to terpolymer；297 DEG C are about 1- with the melt flow index under 5kg load 30g/10 minutes), (melting temperature is about 250 to 275 DEG C to ethylene-tetrafluoroethylene (ETFE) copolymer；Under 297 DEG C and 5kg load Melt flow index be about 1-30g/10 minutes), (melting temperature is about 250 to hexafluoropropene-tetrafluoroethene (FEP) copolymer To 275 DEG C；372 DEG C are about 1-30g/10 minutes with the melt flow index under 5kg load) and tetrafluoroethylene-perfluoro (alkoxy Alkane) (melting temperature is about 300 to 320 DEG C to (PFA) copolymer；372 DEG C are about 1- with the melt flow index under 5kg load 30g/10 minutes).Each in these fluoropolymers can be bought from Dyneon LLC, Oakdale, Minn.TFE-HFP- VDF terpolymers are sold with title " THV ".

The mainly vinylidene fluoride polymer made of interpolymerized vinylidene fluoride monomer, including homopolymer and copolymerization can also be used Thing.This analog copolymer includes those of vinylidene fluoride containing at least 50 moles % and at least one monomer copolymerization, the monomer Selected from tetrafluoroethene, trifluoro-ethylene, chloro trifluoro ethylene, hexafluoropropene, vinyl fluoride, pentafluoropropene and it is easy to and vinylidene fluoride Any other monomer of copolymerization.These materials are also described in United States Patent (USP) 4,569,978 (Barber), which passes through reference It is incorporated herein.Preferable copolymer is by least about 70 at most 99 moles % vinylidene fluoride and corresponding about 1 to 30% Tetrafluoroethene made of copolymer (as disclosed in British patent 827,308) and by about 70 to 99% vinylidene fluoride With 1 to 30% hexafluoropropene made of copolymer (see, for example, United States Patent (USP) 3,178,399) and rubbed by about 70-99 Copolymer made of that vinylidene fluoride of % and the trifluoro-ethylene of 1-30%.Vinylidene fluoride, trifluoro-ethylene and tetrafluoroethene Terpolymer (as described in United States Patent (USP) 2,968,649) and vinylidene fluoride, trifluoro-ethylene and tetrafluoroethene Terpolymer be also the vinylidene fluoride copolymer class that can be used in the present invention representative example.This kind of material can be with business Name of an article KYNAR from the Arkema Group positioned at Pennsylvania's Jin Gefupu western Shandongs Asia or with trade name DYNEON from Dyneon LLC of Oakdale, MN are bought.Fluorocarbon elastomer material can also be used in the composite material of the present invention.Fluorine polymerize Thing contains VF₂With HFP monomers and optionally contain TFE, and density is more than 1.8g/cm³.Fluoropolymer is to most of oil, chemicals, solvent There is good patience with halogenated hydrocarbons, and there is excellent patience to ozone, oxygen and weather.Its available temperature limit It is -40 DEG C to 300 DEG C.Be described in detail in the United States Patent (USP) 4,257,699 of the example of fluoroelastomer including Lentz those and Those described in the United States Patent (USP) 5,061,965 of the United States Patent (USP) 5,017,432 of Eddy etc. and Ferguson etc..These patents In the disclosure of each by quote be fully incorporated herein.

Latex fluoropolymer can be obtained in the form of the polymer comprising PFA, FEP, ETFE, HTE, THV and PVDF monomer .Being fluorinated poly- (methyl) acrylate usually radical initiator well known to those skilled in the art can be used to pass through body or molten It is prepared by agent radical polymerization.It can include (methyl) acrylic acid with other monomers of these fluorination (methyl) acrylate monomer copolymerization Arrcostab, (methyl) alkyl acrylate of substitution, (methyl) acrylic acid, (methyl) acrylic amide, phenylethylene, halogen ethene Class and vinyl esters.Fluoropolymer can include polar component.The monomer of this kind of polar group or polar functionalities can be anion, Nonionic, cation or both sexes.In general, more common polar group or the organic group of polar functionalities include organic acid, Particularly carboxylic acid, sulfonic acid and phosphonic acids；Carboxylate, sulfonate, phosphonate, phosphate, ammonium salt, amine, acid amides, alkylamide, alkyl Aryl amide, acid imide, sulfonamide, methylol, mercaptan, ester, silane and polyoxyalkylene, and other organic groups are such as The alkylidene or arlydene substituted by one or more this kind of polar groups.Latex fluoropolymer specifically described herein is usual It is water dispersible solid, but solvent material can be used.Fluoropolymer can form lotion, solution or liquid form with various solvent combinations Dispersion.The dispersion of fluoropolymer can be prepared with conventional emulsion polymerization method, such as United States Patent (USP) 4,418,186,5,214, 106th, 5,639,838,5,696,216 or John scheirs are (special in the Modern Fluoropolymers of editor in 1997 71-101 and 597-614 pages) and submit on January 31st, 2001 assignee while unexamined patent application sequence number 01/ Described in 03195.

Liquid form can also reach required concentration through further dilution.Although aqueous emulsion, solution and dispersion are excellent Choosing, but at most about 50% cosolvent such as methanol, isopropanol or methyl perfluorobutyl ether can be added.Preferably, aqueous emulsion, molten Liquid and dispersion include the cosolvent of the cosolvent below about 30%, more preferably less than about 10%, most preferably aqueous emulsion, solution and The basic co-solvent of dispersion.

The classification for the interface modifier cover extensively used in the application, including such as stearic acic derivative, silane chemical combination Thing, titanate compound, zirconic acid ester compounds, aluminic acid ester compounds.The selection of interface modifier by metallic particles, polymer and Using decision.The maximal density of composite material is the function of density of material and each material volume fraction.The composite wood of higher density Material is obtained by making per unit volume that there is the material of most high-density to maximize.The material is only almost refractory metal such as tungsten Or osmium.These materials are especially hard and are difficult to deform, and often result in brittle fracture.When with deformable polymer adhesive mixture, These fragile materials can be formed as useful shape with traditional thermoplasticity device.But obtainable maximal density will be less than most preferably Value.When forming the composite material for the excluded volume that polymer volume is approximately equal to filler, intergranular interaction will dominate material The behavior of material.Particle is in contact with each other, the sharpened edge of interaction, soft surface (causing chisel to be cheated, to put often processing hardening) Friction between combination and surface further prevents optimal accumulation.Therefore, maximized performance be Surface softness, edge hardness, The point size (acutance) of point, skin-friction force and pressure, circularity and common shape on material, the function of Size Distribution. Due to this intergranular friction, forming pressure will exponentially be reduced with the distance with being exerted a force.Interface modification chemical energy leads to Cross the surface of the combination modified densification filler of coordinate bond, Van der Waals force, covalent bond or this all three.The surface exhibits of particle For the particle of the non-reactive end of interface modifier.These organic matters reduce intergranular friction, so as to prevent chisel from cheating and allow particle Between bigger freedom of motion.These phenomenons make applied plastic force deeper can reach inside configuration and cause evenly Barometric gradient.

Stearic acid compound is modified the composite material of the present invention, in surface of metal particles the formation of stearic acid layer reduce molecule Between power, improve the tendency that is mixed with metallic particles of polymer and increase composite density.Similarly, silane interface modifier By metallic particles and continuous polymer it is alternate form chemical bond or surface energy by varying inorganic metal particle be allowed to The surface energy polymer of particulate polymers interface matches and improves the physical property of composite material.It can be used in the present invention Silane coupling agent includes but not limited to the compound such as lower structure：

R-(CH₂)_n-Si-X₃

Wherein X represents hydrolyzable group, including alkoxy, acyloxy, halogen or amine, the surface depending on metallic particles Chemistry and reaction mechanism.Coupling is maximized with the maximization of chemical bond quantity between particle surface and polymer.Work as composite material During by the application that be used to include a large amount of aqueous mediums and wide range of temperature, both arms silane (dipodal is selected Silane) such as double (triethoxysilyl) ethane.These materials have such as lower structure：

R[(CH₂)_n-Si-X₃]₂

Wherein R represents the non-hydrolysable organic group of silane compound.R group is chemically bonded to polymer phase or such as Unreacted is then kept if the interface modification of fruit nonbonding is applicable as desired.When R is chemically bonded to polymer phase, this A little free radicals can be added by heat, light or in the form of peroxide catalyst or accelerating agent and similar reaction system.In addition R bases The selection of group need to consider the polymer used in composite material.If selecting thermosetting polymer, thermosetting polymer can use To be chemically bonded silane to polymer phase.Active group in thermosets may include methylacryloyl, styryl or The other insatiable hungers of person and/or organic material.

Thermoplastic includes polyvinyl chloride, polyphenylene sulfide (polyphenylene sulfite), acrylic compounds homopolymerization Thing, the polymer containing maleic anhydride, acrylic material, vinyl acetate polymer, copolymer (such as 1, the 3- fourths two containing diene Alkene, Isosorbide-5-Nitrae-pentadiene), the polymer that is modified of halogen or chlorosulfonyl or can with the composite system reaction of the present invention its Its polymer.Contracting can be used with aminoalkyl, chlorine alkyl, isocyanate group or the silane reaction of similar functional group by end group Heat build-up plastic material, including polyamide, polyester, makrolon, polysulfones and similar polymeric material.

The production of high desnity metal particulate composite depends on good production technology.Usual metallic particles is first through interface Modifying agent such as reactive silane is handled, and way is in metal with the silane of 25 weight % or the solution spraying of other interface modifiers On particle and it is blended with carefully drying to ensure the uniform coated particle of interface modifier.Height can also be used in interface modifier such as silane Intensity Littleford or Henschel blender are added in particle in batch blending (bulk blending) operation.As Selection, can be sent into duoble cone-type blender before the drying, or be applied directly in screw rod mixing device.Interface modifier also can be non- Reacted in proton solvent such as toluene, tetrahydrofuran, petroleum solvent or other this kind of known solvents with metallic particles.

Metallic particles can be coupled with polymer phase, depending on the property of polymer phase, filler, particle surface are chemical and compound Any pigment processing aid or additive present in material.In general, for being coupled the mechanism of metallic particles and polymer Including solvation, chelating, coordination bonding (ligand is formed) etc..Titanate esters or zirconium ester coupling agent can be used.This kind of coupling agent tool There is 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.Titanate esters, which provide inoxidizability, can simultaneously be modified or controlled curing chemistry.Zirconate provides excellent Different bond strength and maximize curing, reduce and form color in the thermoplastic of preparation.Useful zirconate materials For neopentyl (diallyl) oxygen-three (dioctyl) phosphate-based zirconate.

High desnity metal polymer composites with required physical property can be by following productions.In preferable mode In, surface of metal particles is first prepared, interface modifier is reacted with obtained granular materials, separating obtained product, then with connecting Continuous polymer phase is combined to be reacted with being realized between metallic particles and polymer.Once being prepared for composite material, it is then by shape As the shape needed for final use material.Another program is the solution processing that solvent recovery is provided in material processing. Material also can be solvent-free dry-mixed.Can be used blending system Tathagata from the ribbon formula mixing machine of Drais Systems, from The high density driving mixing machine that Littleford Brothers and Henschel are obtained.Also can use using Banberry, Other melt blendings of veferralle single screw rods or twin screw compounder.When material is as the plastisol with solvent or organic When colloidal sol is processed, liquid component is usually first added in processing unit (plant), is then added polymer, metallic particles and is quickly stirred. Once add all material, can applying vacuum with remove remnants air and solvent and continue mixing until product uniformly and obtain High density.

Due to cost advantage, it is usually preferred to dry-mixed.But some embodiments may due to particle diameter difference and in composition It is unstable.In dry mixing process, composite material can be made by the steps：Polymer is first introduced, if necessary in about room temperature To merging polymer stabilizer and the polymer, blending metallic particles (if necessary to modified) and institute at a temperature of about 60 DEG C State through stable polymer, blend other processing aids, interface modifier, colouring agent, indicator or lubricant, it is then mixed in heat Mixed in clutch, be transferred to storage, packaging or final use production.

The material of interface modification can be prepared with solvent technology, and the solvent technology triggers composite wood using a effective amount of solvent The formation of material.When interface modification is basically completed, solvent can be stripped out.This kind of solvent method is performed as follows：

1) interface modifier or polymer or the two solvation are made；

2) metallic particles is mixed into body phase or polymer master batch；With

3) volatile ingredient in sloughing composition at a temperature of higher than polymer Tg in the presence of heat and vacuum.

When with twin screw compounder or extruder mixture, it can be used and be related to the selection process that double-screw mixing is matched somebody with somebody as follows.

1. add metallic particles and heat up and remove surface water (machine barrel 1).

2. interface modifier (machine barrel 3) is added into twin-screw when filler is in appropriate temperature.

3. the dispersion/distribution interface modifier on metallic particles.

4. maintain reaction temperature to react complete.

5. discharge byproduct of reaction (machine barrel 6).

6. add polymer adhesive (machine barrel 7).

7. compression/molten polymer adhesive.

8. dispersion/distribution polymer adhesive in the grain.

9. modified particles are made to be reacted with polymer adhesive.

10. pair remaining reaction product vacuum outgas (machine barrel 9).

11. compression gained composite material.

12. required shape, pellet, wire rod, pipe, injection-molded item etc. are formed by step after die head or production.

Alternatively, in the formula of the continuous phase containing small size：

1. add polymer adhesive.

2. interface modifier is added into twin-screw when polymer adhesive is in appropriate temperature.

3. the dispersion/distribution interface modifier in polymer adhesive.

4. add filler and dispersion/distribution particle.

5. it is warming up to reaction temperature.

6. maintain reaction temperature to react complete.

7. compression gained composite material.

8. required shape, pellet, wire rod, pipe, injection-molded item etc. are formed by step after die head or production.

Polymer allows to save interface modifier and its related procedure of processing to the specific selection of particle.

The metal polymer composite of the present invention can be used for multiple embodiments, including projectile, bait, fishing pendant, automobile Balance weight, radiation shield, golf pole member, sports equipment, gyro ballast (gyroscopic ballast), mobile phone vibrations The weight of balance weight or laboratory barrier noise and vibrations other is needed with plasticity, toughness and dimensional stability, heat conduction In property, electric conductivity, magnetism and the embodiment of nontoxic high density material.

The high density material of of the invention and its all embodiments is suitable for a variety of processing methods.Processing method and basic material The selection of material formula can the needs based on required final use product.The following examples will be illustrated this point.

One embodiment of the invention is available for projectile (including musket bullet and other ammunitions), heart or artery With the flexible or malleable composite material in stent or radiation shield clothes.Exemplary composite material with these features may include The combination of tungsten, the fluoropolymer as adhesive and zirconate interface modifier.Final use product can be extrusion or moulding Product.

Another embodiment of the present invention is available for bait or fishes in pendant or mobile phone shielding or internal vibration mechanism High yield, high density composite.Exemplary composite material with these features may include tungsten, the polyvinyl chloride as adhesive With the combination of alkali metal stearic acid salt or stearmide interface modifier.Final use product can be the production of extrusion or moulding Thing.

The another embodiment of the present invention be available for automobile or truck inflation tire wheel balance weight or other ballasts or It is other can with block form produce product in low yield, long hardening time and high density composite.With these features Exemplary composite material may include the combination of tungsten, the polyester as adhesive and zirconate interface modifier.Final use product It can be the product of injection or block molded item.

A further embodiment of the invention is to balance height in the block available for bait and automobile or truck inflation tire wheel Production, high density composite.Wheel balancing block includes the product block of annex and composite material of the present invention.Balance weight can use conventional folder Connection is adhered on wheel with adhesive.Exemplary composite material with these features may include tungsten, as adhesive The combination of polystyrene and zirconate interface modifier.Final use product can be the product of injection or block molded item.

In addition to foregoing example embodiment, other processing methods are but are not limited to：Molding, compression moulding, thermosetting property and thermoplastic Property extrusion, centrifugal modling, rotational molding, blowing, casting, calendering, liquid filled thermoset molding or filament winding, with order Mixture forms variously-shaped together.Another embodiment of the present invention includes the magnetic composition of gained composite material, wherein for Identification or as final use requires defined, adds magnetic component.Magnetic additive accounts for the weight and body of gained composite material Fraction is usually 0.1% to 5%.

A further embodiment of the invention includes the coloring of gained composite material, wherein for identification or as final use will Ask the color of defined critically important.The weight and volume fraction that color additives account for gained composite material is usually less than 1%.

The composite material of the present invention can be used in projectile in the form of musket bullet or shaping roundel.Musket bullet leads to Often it is spheric granules, size is about 0.7 to about 3 millimeters and typically spherical, but can have drawn grain or pitted skin.

The projectile that can be used in the present invention generally comprises significant percentage of high density composite of the invention.Projectile can Include the extrusion bar of jacketed or not jacketed form.Chuck can surround composite material or can to leave a part of (front end or rear end) naked Expose outside.Composite material can produce to form projectile in many ways.Projectile can include about 0.1 gram to up to 2 kilograms it is of the invention Composite material, the composite material are at least partly surrounded by metal chuck.This kind of projectile can have cone-shaped open formula front end, opening Formula blind end or the two, or can entirely be encapsulated in chuck.In addition, chuck may include other components such as explosive, ferrule or its Its 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.By the present invention The composite material comprising tungsten, iron or other nontoxic metals made from this kind of projectile form " green " bullet or projectile, it makes The non-toxic material compatible with water plant and animal is degenerated to after.The elastic performance of material makes projectile particularly useful.Due to it High density, projectile can transmit sizable inertia or kinetic energy to target, but equally contact when elastically deformable and as plumb that Sample expands chuck.Chuck will expand as expected, but elastic material will recoil to its original dimension substantially.

Roundel or projectile may be designed as making Pneumatic pressure center and center of gravity or barycenter can to the front portion of sized central or after Portion is adjusted to improve the aeroperformance of roundel.This kind of roundel can be fabricated to more stable ballistic flight and avoid deviateing institute Desired trajectory and reduction accuracy.Further, since its stability, material of the invention can be launched with the emissivity of higher and by Reduce in the speed of rotation and reduce weapon heat.In the preferred projectile of the present invention, center of gravity is located at Pneumatic pressure center well It is preceding and just by rotating roundel stabilization in its targeted trajectory.

In short, pointed by specific rights requirement as embodied herein, the present invention relates to a series of material combinations, The material combination includes metal, polymer, interface modifier and other additives, it is respectively provided with different particle diameters, weight point Number and volume fraction.Should present invention additionally comprises a series of processing methods, the physics of gained and chemical property and final use With.Following material is the illustration to the present invention.The material can shape, mold, extrude or be made useful compound Material and shape.

Experiment 1

Experiment is primarily upon aspect by three and forms：Density, melt flow index, tensile strength and elongation.Density is surveyed The fixed extruded technique of device by using Wild River Consulting assemblings produces sample and carries out, described device mainly by It is equipped with 1 of the transformation in the hole with 0.1 inch diameter in the metallurgical forcing press and underarm of measuring cell¹/₄Inch cylindrical die head Composition.Assuming that the sample produced by these instruments is in perfectly round cylinder, therefore measure average diameter, length and quality can Obtain the density of sample.

The melt flow index of each sample is measured in die head extrusion.By determination sample, by instrument, (instrument is By extrusion lengthy calibration) on time of mark can calculate its rate of extrusion.Then divided by aperture normalizes the linear velocity. The amount of gained is defined as the melt flow index (MFI) of material.To ensure to be thoroughly mixed, the material of extrusion extrudes at least four again It is secondary.

Also test the tensile elongation of die head extrusion sample.Each sample is trimmed to it is 4 inches long, and away from each end¹/₂Inch Mark at place.Sample is fixed in the fixture of instrument, wherein¹/₂Depth in inch mark sample insertion fixture.Stretched Fracture is tested and removes sample in the completed.

Test uses Alldyne C-60 tungsten and two kinds of formulas of Dyneon THV220A fluoropolymers in experiment.The first Formula is designed as obtaining 10.8g/cm³Density.Second of formula is designed as obtaining 11.4g/cm³Density.Table 1 provide for Produce the percetage by weight used in the sample of two kinds of formulas.Four kinds of interface modifiers are tested in experiment.The first interface modification Agent is zirconium ester coupling agent NZ 12.Second and the third modifying agent are titanate coupling agent KR238J and LICA09.It is last a kind of Interface modifier is silane SIA0591.0.

Composite Melt is flowed the different interface modifiers of table 1 and the influence of mechanical performance

* the interface modifier of 0.2 weight % is contained

It will be clear that the processing of tungsten powder causes the sizable change of physical property.In all formulas, interface changes The processing of property agent significantly affects melt flows.The melt flow index of compounded materials is high compared to the increase of undressed compound Up to 68 times.Also its influence can be seen in the elongation of material.All four interface modifiers cause the increasing of tensile elongation Greatly, change is maximum caused by wherein NZ 12 and KR238J.Although the material handled through SIA0591.0 does not show melt flows The increase of index, but it shows the increase of maximum stress really.SIA0591.0 compounded materials produce maximum stress be about Three times of the tungsten compound of the 91.4 weight % without interface modifier.

Experiment 2,3 and 4

In table 2,3 and 4, tungsten particle is first handled with interface modifier.This passes through very small amount of interface modifier is molten Progress is mixed in solvent (being often isopropanol or some other alcohol) of the solution in beaker and in beaker with tungsten particle.Gained slurry Then it is thoroughly mixed about 10 minutes.Substantially it is decanted off solvent or in about 100 DEG C of evaporation of solvent.Particle and then again in an oven It is dry.Individually by polymer (such as) THV220A is dissolved in solvent (such as acetone).Then by the processed tungsten of appropriate weight Grain is added in the polymer of dissolving, and stirring mixture is until most of solvents have evaporated and mixture has been reunited.Material is in 100 DEG C It is 30 minutes dry, then suppressed in metallurgical mould.

THV200A is the polymer of tetrafluoroethene, hexafluoropropene and vinylidene fluoride.NZ 12 is neopentyl (two allyls Base) phosphate-based (phosphato) zirconate of epoxide-three (dioctyl).SIA0591.0 is N- (2- amino-ethyls) -3- amino Propyl-trimethoxy monosilane.KR 238J are the methyl that can be obtained from Kenrich Petrochemicals, Bayonne, NJ Acrylic amide modified amine adduct.LICA 09 is neopentyl (diallyl) epoxide-three (dodecyl) benzene-sulfonyl-metatitanic acid Ester.

Influence of the interface modifier of 2 various concentrations of table to the density and mechanical performance of fluoropolymer composite

Influence thermoplastics (PVC) of the 3 interface modifier NZ 12 of table to PVC polymer density and mechanical performance

Thermosets (polyester)

The annotation of table：

(1) one is removed from the molds and crushes.

As seen from the table, multiple polymers, which can be used to prepare density, is higher than 10g/cm³And with useful viscoelastic multiple Condensation material.

Influence of the particle diameter and circularity of 4 tungsten of table to density

* 12 interface modifiers of NZ containing 0.03-0.2%

These as shown by data thermoplastic composites in table can be prepared and including density, mould with selected combination of materials The degree of the performances such as amount, elongation can be designed into material.

The table shows that particle diameter, distribution and circularity have an impact the density of composite material.The preparation of these materials a-g and reality It is similar to apply a 1-16.All samples in table 4 are prepared as the composite material for making formula produce most high-density.Since there are larger With small mean size particle materials and about 14 smallest circular degree, therefore material b and e have maximal density.Material a and c have in table There is low-density and there is small or big particle.Other materials make slightly offset from (material b's and e) size or circularity parameter Density reduces.

Experiment 5

Melt flows experimental data material therefor in table 5 is prepared as follows.Technon Plus tungsten particles are modified, with Dyneon polymer is blended and is incorporated into calibrated gravity-feeder in extruder.Extruder is 0.75 English of Brabender Very little band customization screw thread it is engineered to produce low-compression single screw extrusion machine.Heating zone is arranged to 175 DEG C, 175 DEG C, 175 DEG C With 185 DEG C.Screw speed is maintained between 20 and 40rpm.Machine barrel is air-cooled.Material outlet speed is about 1 meter per minute.Testing By the Technon Plus tungsten (particle diameter distribution is 10 to 160 microns) and 8 of 92 weight % in the Brabender extruders of room scale The fluoropolymer Dyneon THV220 of weight % merge, and wherein Dyneon THV220 are with 12 zirconates circle of Kenrich NZ The polymer of face modifier modification.In this embodiment, interface modifier is with the ratio of the about 0.01 weight % on metallic particles It is 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 seconds^-1.To measure melt extrusion flow index, the pilot system of customization is established.To 1.25 inches of metallurgy Aperture (diameter 0.192cm) is bored in mould.Metallurgical mould is applied in combination with the metallurgical forcing press equipped with instrument, so allows to monitor mould temperature And pressure.The temperature of material and the pressure of mould are set, material is extruded by melt flows hole.For the given duration, survey The length of fixed gained body, is as a result used for determining average speed.Using the data, with the speed difference divided by die hole radius of extrudate Melt flow index can be calculated.

Influence density of material of 5 temperature and pressure of table to melt flows 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 is (by weight)：

It is 38 weight % that polystyrene, which is dissolved in the mixture of toluene, methyl ethyl ketone and acetone to total solid,.Stirring It is lower two kinds of particles to be dispersed in identical solvent mixture and NZ 12 is added into the dispersion.TiO is opened in stirring₂Reunite Polystyrene solution is added afterwards and is stirred discharges solvent at the same time until blend is changed into semi-solid.Then the material is compression molded into band The fishhook of No. 1 hook (referring to Fig. 3).

Production of articles embodiment 2

Contain：Polystyrene, Technon powder and Ken-React NZ 12.

Formula is (by weight)：

Polystyrene 0.6011g

Technon PLUS particles 12.0927g

12 0.03g* of Ken-React NZ

It is 38 weight % that polystyrene, which is dissolved in the mixture of toluene, methyl ethyl ketone and acetone to total solid,.Stirring It is lower W particles to be dispersed in identical solvent mixture and NZ 12 is added into the dispersion.Add polystyrene solution and stir Mix while discharge solvent until blend is changed into semi-solid.Then the material is compression molded into sliding pendant (slip sinker).

Production of articles embodiment 3

Contain：Polyester, Technon powder, 2073 TiO of Kronos₂With Ken-React NZ 12.

Formula is (by weight)：

Methyl ethyl ketone peroxide

Polyester is added to W and TiO₂In particle.Acetone is added to help NZ 12 scattered.Start to develop the color in blend Sign (i.e. TiO₂It is scattered) after, more acetone are added, then add methyl ethyl ketone peroxide.The material is compression molded into sliding pendant.

Production of articles embodiment 4

Contain：Polyester, Technon powder, 2073 TiO of Kronos₂With Ken-React NZ 12.

Formula is (by weight)：

Methyl ethyl ketone peroxide

Polyester is added to W and TiO₂In particle.Acetone is added to help NZ 12 scattered.Start to develop the color in blend Sign (i.e. TiO₂It is scattered) after, more acetone are added, then add methyl ethyl ketone peroxide.The material is compression molded into No. 1 sliding pendant.

Production of articles embodiment 5

Contain：Fluoroelastomer, Technon powder and Ken-React NZ 12.

Formula is (by weight)：

Fluoroelastomer THV220A Dyneon 1.6535g

Technon PLUS particles 36.8909g

Ken-React NZ 12 0.0400g

NZ 12 is blended into W particles with the help of acetone.By THV220A dissolvings in acetone to 38 weight %, so After be added in W slurries.The blend is stirred to dry, the then compression moulding in 1.25 inches of metallurgical forcing press.The big pellet is cut Into square and in 104 DEG C of oven dryings to doing, then in 5700lb/in in metallurgical forcing press²With 177 DEG C at reshape.Should The density of material is 11.7g/cm³。

In these embodiments, tungsten particle is first handled through interface modifier.This passes through the desired amount of interface modifier is molten Solution simultaneously and then into beaker adds 100 grams of tungsten in the 250ml beakers of solvent containing 50ml (being often isopropanol or some other alcohol) Particle carries out.Then gained slurry is thoroughly mixed in steam bath until mixture can not be stirred for and most of solvents have driven Go out.Then the beaker containing tungsten particle and interface modifier is placed in 100 DEG C of forced ventilation baking oven 30 minutes.Will be processed Tungsten is added to be dissolved in the 100ml beakers of the solid solution in acetone containing THV220A.Then 30 DEG C and continuous are heated the mixture to Stirring is until most of acetone evaporateds.Then composite material is placed in 100 DEG C of forced ventilation baking oven up to 30 minutes.After drying In 3.17cm cylinders in metallurgical mould composite material is suppressed under 200 DEG C and 4.5 tonnes of circuit die.Allow mould after five minutes 50 DEG C are cooled under stress.After discharging pressure, composite sample is taken out from mould and measures physical property.On composition and Surveyed performance referring to table _.THV220A is the copolymer of tetrafluoroethene, hexafluoropropene and vinylidene fluoride.NZ 12 is neopentyl (diallyl) epoxide-three (dioctyl) phosphate-based zirconate.SIA0591.0 for N- (2- amino-ethyls) -3- aminopropyls - Trimethyoxysilane.KR 238J are the methacryl that can be obtained from Kenrich Petrochemicals, Bayonne, NJ Amine is modified amine adduct.LICA 09 is neopentyl (diallyl) epoxide-three (dodecyl) benzene-sulfonyl-titanate esters.

Prepare as described above a series of % of weight containing 0.1-0.2 12 THV-220 of NZ and metallic particles it is exemplary Material.

Table 6

Embodiment of the various metals under different metal loading

Monometallic composite material

Maximum filling lower density=4.5 of the double metallic composite material 90%

Table 6 provides a series of monometallic polymer composites that metal filled amount is 47-90 volume % metals.In table Different metallic composites is provided by the metal-containing polymer composite wood of the metal filled amount containing the percentage by volume in each row Expect the composite density obtained.As seen from the table, for various metals, the metal in the density and composite material of composite material Percentage by volume it is directly proportional.For example, as metal volume percentage composition or loading increase to 90 volume %, tungsten from 47 volume % Composite density changes to about 18 from about 10, and the increase for each density metal is similar.

Volume filling and the density characteristics of the composite material of the present invention are graphically provided in Figure 28,29 and 30.Figure 28 In draw volume filling and the relation of density of stainless steel, bismuth and composite tungsten material.Data in Figure 28 are derived from table 6, show close Degree is linearly increasing relative to volume filling, such as the data prediction from table.Zinc, palladium, copper, tantalum, osmium, stainless is drawn in Figure 28 The relation of metal volume percentage in steel, the final densities of bismuth and composite tungsten material and composite material.Equally, (the table 6 such as from table In data) prediction as, the density of composite material increases with the increase of metal volume percentage in composite material.Figure 30 Show with about 45% until about 90% volume filling obtains the maximal density of composite material of the present invention.The maximal density of acquisition is About 20-21g/cm.

We have been examined by material property and two kinds of metals of the present invention are evaluated, measure and characterized to instrument analysis technology The heat and viscoplasticity of polymer composites.These performances have no in the prior art.Generally, prior art material fails to obtain True composite characteristics are obtained, therefore the true viscous-elastic behaviour and thermal conduction characteristic of true composite material cannot be obtained.This kind of material is crisp, cannot Extrusion molding or injection and cannot reach high heat conduction level.

The hot property of the material of the present invention is unique.Although the material is metal polymer composite, this is multiple The hot property of condensation material is rather than more polymer-like more like metal.When in heat transfer applications, thermal conductivity factor can be more 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 viscoplasticity, tensile elongation and slit die rheological technique are used.Viscosity measure passes through during melt-processed Han slit dies on Haake single screw rod torque rheometers carry out.The viscoelastic characterization of extrusion sample passes through Chatillon LFPlus uniaxial tensile elongation rates tester is completed.The purpose of experiment also attempts to establish viscosity/viscoelastic between two kinds of composite materials Property the difference that can characterize or confirm that two kinds of materials have identical viscosity/viscoelasticity.The two kinds of materials to compare be have it is similar It is formulated but prepares the composite tungsten material different with service life.

Composite material discussed below is used during characterization.Two kinds of composite materials prepare and using about as described above substantially The interface modifier of 0.1-0.2 weight %.The material analyzed in Table A-H and Figure 12-20 mainly by tungsten or other metallic particles with THV220 is formed, density 11.4g/cm³, it corresponds to two kinds of composite materials containing about 56 volume % tungsten powders.The master of storeroom Difference is wanted to be that a kind of material is by tungsten and THV220 only mixtures once granulating, and another material is mixed by cyclic process Match somebody with somebody.Cyclic process is made of multi-step process, and the wherein formation of material includes at least following steps：By the tungsten through interface modification and THV220 mixtures is pellets, with the THV220capstock coextrusion of coloring, in comminutor, chopping, mixture return pellet and and tungsten Mixture is to obtain specific density.The only material of mixture once will be referred to as " original material ", and the material of multistep mixture will be claimed For " reprocessing material ".This shows original material with unique heat and viscous-elastic behaviour and reprocessing material is with identical property Energy.

Make the about 800ml loose materials of each composite material respectively by Haake torque rheometers.Haake rheometers have interior Footpath is one inch of bobbin and is set as 140 DEG C of three humidity provinces.Han slit dies are connect on to torque rheometer, slit die tool There are the about rectangular section of 2.0mm × 20.00mm and about 75 shaping segment lenght, rheometer is squeezed with three determination of pressure sensor The pressure of melt flow during going out.Two heating tapes are connect to seam, the setting value of the two is controlled as 140 DEG C.Haake slit dies are soft Part calculates the shear stress of material by the pressure drop measured along three points inside slit die.Slit die software requirement is extrusion test journey Sequence inputs lower and upper limit.The lower limit of RPM is arranged to 5rpm, and the upper limit is arranged to 100rpm.Haake softwares then bound it Between select 8 rpm setting values to be shared in test program to 10 rpm setting values.Span exceedes the screw rod of an order of magnitude Range of set value represents wider technological operation scope.Rheometer can under each rpm setting values automatic running.When Haake is being squeezed When going out, extrudate generation sample is cut after extruding 60 seconds.Then the weight of sample extrudate is weighed and by gained weight typing In Haake.The body of each rpm setting values is calculated by software using the example weight and the composite density that is previously entered of input Product output valve.Note that software does not allow to input 11.4g/cm³This density, therefore 1.14 this value are inputted, therefore all samples weight Measure input value divided by ten with compensation density scalar.Software calculates the shear rate in slit die with volume output valve.

Haake evaluation softwares are run after the completion of all screw speed setting values are equal, original output is transfused to electronics examination In calculation table and then to the map data that is collected into.It is 11.4g/cm by Haake softwares and operating personnel³Original material first Wheel collects initial data.Listed rpm setting values are selected by Haake softwares, except minimum and maximum value.Pressure 1,2 and 3 by positioned at Melt force sensor measure in Han die slots.Enter the melt pressure of material before slit die at the screw head by labeled as P0 Determination of pressure sensor.Shaft torque and melt temperature are by Haake rheometer measurements.Mass flowrate in extrusion by taking 60 seconds samples measure.Volume flow rate mass flowrate divided by density calculate.

Table A

To analyze 11.4g/cm³Original material, pass through Haake softwares calculate output valve.Shear rate, shear stress and Viscosity is calculated by Haake softwares with the value presented in table B.

Table B

It is the second wheel 11.4g/cm by Haake softwares and operating personnel³Original material collect initial data.Listed rpm Setting value is selected by Haake softwares, except minimum and maximum value.Pressure 1,2 and 3 is passed by the melt pressure in Han die slots Sensor measures.Shaft torque and melt temperature are by Haake rheometer measurements.Mass flowrate is by 60 seconds samples being taken in extrusion Product measure.Volume flow rate mass flowrate divided by density calculate.Some values are paid attention to without Haake software records or display, therefore It is not presented in table C.

Table C

For second of analysis 11.4g/cm³Original material, pass through Haake softwares calculate output valve.Shear rate, shearing Stress and viscosity are calculated by Haake softwares with the value presented in table D.Notice that the value lacked in table D causes the sky in the table In vain.

Table D

It is third round 11.4g/cm by Haake softwares and operating personnel³Original material collect initial data.Listed rpm Setting value is selected by Haake softwares, except minimum and maximum value.Pressure 1,2 and 3 is passed by the melt pressure in Han die slots Sensor measures.Shaft torque and melt temperature are by Haake rheometer measurements.Mass flowrate is by 60 seconds samples being taken in extrusion Product measure.Volume flow rate mass flowrate divided by density calculate.

Table E

To analyze 11.4g/cm for the third time³Original material, pass through Haake softwares calculate output valve.Shear rate, shearing Stress and viscosity are calculated by Haake softwares with the value presented in table F.

Table F

It is analysis 11.4g/cm by Haake softwares and operating personnel³Reprocessing material collect initial data.Listed rpm Setting value is selected by Haake softwares, except minimum and maximum value.Pressure 1,2 and 3 is passed by the melt pressure in Han die slots Sensor measures.Shaft torque and melt temperature are by Haake rheometer measurements.Mass flowrate is by 60 seconds samples being taken in extrusion Product measure.Volume flow rate mass flowrate divided by density calculate.Some values are paid attention to without Haake software records or display, therefore It is not presented in table.

Table G

To analyze 11.4g/cm³Reprocessing material, pass through Haake softwares calculate output valve.Shear rate, shear stress Calculated with viscosity by Haake softwares with the value presented in table H.

Table H

Figure 12 is to 11.4g/cm³Original and reprocessing material provide the quality of extrudate under different screw speeds (rpm) Flow rate calculation value (g/min).The data that original material is respectively taken turns are derived from Table A, C and E.The data of reprocessing material are derived from table G.

Figure 13 is to 11.4g/cm³Original and reprocessing material provide and be applied under different screw speeds (rpm) on screw rod Torque value (Nm).The data that original material is respectively taken turns are derived from Table A, C and E.The data of reprocessing material are derived from table G.

Figure 14 is to 11.4g/cm³Original and reprocessing material provide under different screw speeds (rpm) material in extrusion The shear rate calculated value (1/s) of material.The data that original material is respectively taken turns are derived from table B, D and F.The data of reprocessing material are derived from table H。

Figure 15 is to 11.4g/cm³Original material provide the melt of material in extrusion under different screw speeds (rpm) Pressure measuring value.A class value corresponds to P1 sensors above, and set below value corresponds to P3 sensors.The number that original material is respectively taken turns According to being derived from table B, D and F.The data of reprocessing material are derived from table H.

Table 16 is to 11.4g/cm³Original material provide the shearing of material in extrusion under different screw speeds (1/s) Stress calculation value (Pa).The data that original material is respectively taken turns are derived from table B, D and F.The data of reprocessing material are derived from table H.

Figure 17 is to 11.4g/cm³Original material provide under different screw speeds (1/s) the apparent of material in extrusion Viscosity calculations value (Pa*s).The data that original material is respectively taken turns are derived from table B, D and F.The data of reprocessing material are derived from table H.

Figure 18 is to 11.4g/cm³Original material be given under the shear rate (1/s) of calculating material in extrusion Shear stress calculated value (Pa).The data that original material is respectively taken turns are derived from table B, D and F.The data of reprocessing material are derived from table H.

Figure 19 is to 11.4g/cm³Original material be given under the shear rate (1/s) of calculating material in extrusion Apparent viscosity calculated value (Pa*s).The data that original material is respectively taken turns are derived from table B, D and F.The data of reprocessing material are derived from table H.

Figure 12 provides answering for the tensile elongation from the first and second wheel original materials and the sample for reprocessing material wheel Power (MPa) and strain (%) result.By the sample of extrusion be cut into ASTM638-4 dog bone-shaped sample and with 25mm/min stretching until Rupture failure.

As shown in Figure 12, the mass flowrate of extrudate for screw speed until 40rpm situation it is roughly the same, it is described Mass flowrate is measured by cutting the length of material of 60 seconds duration of extrusion.From Figure 12 it is also seen that for screw speed Situation higher than 40rpm, the mass flowrate between respectively taking turns start difference.Notice that all three-wheels of 11.4 original composite material come It is from the material of same batch but tested under independent occasion.The change of extrusion material quality flow is most-likely due to work as extruder Material is leaked out caused by mould rear portion when speed increases.More specifically, material leaks out the joint between extruder and Han slit dies. As screw speed increases, there are more materials to leak out.Material leakage is most prominent in the 2nd of original material the and 3 wheels.

Due to associating not for three-wheel original material, the mass flow of material and subsequent volume flow and screw speed Unanimously, therefore the value derived from volume flow rate also should not be related to rpm in three-wheel.This non-correlation is explained maps when to screw speed When each wheel between shear stress, shear strain and apparent viscosity difference.The shortage of this correlation can be seen in Figure 14 and 17.

11.4g/cm³The result that provides of reprocessing composite material and 11.4g/cm³Original composite material the 1st wheel most It is alike.As shown in Figure 12, the mass flowrate for giving material under flow rate is reprocessing most phase between material and the 1st wheel original material Seemingly.As shown in Figure 14, the material is also similar by the subsequent shear rate of Han slit dies.

It is similar between all wheels that the torque on screw rod is applied in extrusion.Fig. 2 shows that although all material is equal It is similar, but when screw speed is higher than 40rpm, there are fine difference between each wheel.

As can be seen from Fig. 15, two kinds of materials show pressure drop identical in depanning.Three original materials and reprocessing material There is no visibly different pressure gap trend or amplitude between material.The calculating of the shear stress of 1st and 2 wheels is by being accomplished manually, reason It is that the calculating that evaluation software is made is that the sensor specified with mistake carries out.1st and 2 wheel sensor P0, P1 and P3, and the 3 wheels use sensor P1, P2 and P3.It is the sensor after mould to pay attention to P0, and P1 is the first pressure point in mould, and P2 is second in mould Pressure spot, P3 are the 3rd pressure spot in mould.Pressure spot P0 cannot be used for calculating the pressure across seam not in slit die Drop.Since the value of P0 is at least twice of P1 values, therefore shear stress values can be higher than right.3rd wheel is right value, the reason is that its Based on across mould pressure drop calculated and without using the P0 recorded.

The 11.4g/cm provided in table B and D³Original material the 1st and 2 wheel apparent viscosities the result is that manually determine , the reason is that specifying P0 as one of pressure in the calculating of evaluation software.3rd wheel provides accurate viscosity output valve, it can Found in table F, it is almost overlapping with the analog value of visible 11.4 reprocessing material in table H.Apparent viscosity and screw rod speed Relation between degree can be seen in fig. 17.Had differences between each wheel, this is because above-mentioned cause because of mould joint material leakage Screw speed and shear rate between relation it is inconsistent caused by.When directly being mapped with apparent viscosity to shear rate, such as In Figure 19, it was observed that all four groups of data are overlapping.Between the three-wheel original material and reprocessing material wheel, in method Measurement capability on there is no marked difference.As shown in Figure 18, the shear stress of storeroom and shear rate have differences.Except original All wheels outside second wheel of beginning material follow similar trend.

Original and reprocessing storeroom tensile elongation is very close.As shown in Figure 20, the stress-strain of each material Characteristic is difficult to differentiate each other.Although the breaking strain % of reprocessing material seems obvious lower, should between same sample The difference of change is about ± 25%.It is more identical for all wheels along the stress of strain paths.Experiment two kinds of materials of proof Viscosity and viscoplasticity can characterize.It is but original in measurement capability there is no difference between reprocessing composite tungsten material.This shows material The recombination property of material is the fundamental property of composite material, can't be simply because material is extruded or reprocessed again and is lost Go.

One of key physical properties surveyed per class material are to be applied between deformation caused by the power on material and the power Relation.The ad hoc fashion of the power applied under the situation is the uniaxial tension of the linear deformation under constant rate of speed.Since sample exists Extended during this because of the drawing force applied, so performance test is often simply referred as " tensile elongation ".The mesh of this document Be to limit the key parameter of tensile elongation test method and analysis and then compare the performances of two kinds of composite materials.

Can be that the test method defines some Key Terms.Figure 21 be under tensile elongation material property with regard to stresses typical- Typical curve for coping behavior, it has made crooked for illustrative purpose.

First term of definition is stress (σ), it is the initial cross sectional product for the power divided by sample being applied on sample. The power being applied on sample is single shaft, axially vertical (bidimensional is vertical) of cross section and power.

Second term of definition is strain (ε), its increase divided by initial sample length for sample length.The normal table of the amount Percentage is shown as, wherein the sample in 100% strain is twice of its initial length.

3rd term of definition is the ε in Figure 21_AIn letter " A ".Behind the opposite linear part of load-deformation curve The drastically decline of stress irreversible transformation by sample causes.Stress value at the point is defined as upper yield stress.Although sample The acutance at the peak may be different between product, but that define the value is local maximum (local maxima).

4th term of definition is the ε in Figure 21_BIn letter " B ".Bent on as caused by irreversible plastic deformation After clothes point, the stress needed for constant strain speed is maintained to start to increase at leisure.Caused local minimum (local Minima) stress value at place is defined as lower yield stress.Stress level is begun to ramp up after the point, usually linear increase.

5th term of definition is the ε in Figure 21_CIn letter " C ".Destroying sample stress when (fracture) starts can be in Another existing local maximum.The point is defined as fracture strength, is often the maximum stress level being applied on sample.Since it is Cause the amount of the stress needed for destroying, therefore it is commonly referred to as " tensile strength " of material.

6th term of definition is the ε in Figure 21_DIn letter " D ".When sample is broken, the power applied becomes immediately It is zero.Deformation values at the point are defined as breaking strain %.

7th term of definition is the ε in Figure 21_EIn letter " E ".Before surrender, stress and strain is substantial linear Relation.Exactly this part deformation makes material show as elasticity.The line is defined as the elasticity modulus of material with the slope of unit of stress Or abbreviation modulus.In these data, term sequence ε_A、ε_B... refer to a series of strain points of strain % increases；ε_A＜ ε_B；ε_C＜ ε_D Deng.It is true composite material to show the characteristic material, obtain the optimal viscoplasticity of polymer and the density of metallic particles, Hot property, electrical property etc..The packing material of the prior art is although fine and close but without such viscous-elastic behaviour or thermal characteristics.

Two kinds of different materials are tested during tensile elongation.The first material for NZ-12 interface modifications tungsten with The composite material of THV220.The grain shape of tungsten is subcircular but irregular and rough and uneven in surface.Formula is containing 60 volume % through processing Metal powder, its 1 volume % about lower than closest packing.For the purpose of this experiment, matching somebody with somebody in 1 volume % of closest packing Side will be referred to as the closest packing (functional closest packing) that works.The density of the material is about 11.9g/ cm³。

Second of material is the 316L stainless steels of NZ-12 interface modifications and the composite material of THV220.The particle of stainless steel Shape is spherical (aerosolization), containing some association particles, almost without anomalistic object.Formula contains the 62 processed gold of volume % Belong to powder, it is also prepared with closest packing.The density of the material is about 5.5g/cm³。

Two samples are extruded by the single screw extrusion machine of the diameter 1 " equipped with 3mm × 20mm rectangle patterns.Extruder Condition is about 135-145 DEG C and 1000psig.The band for being about 6 inches each extruded is used for punching press ASTM 638-4 dog bone-shaped Sample is to carry out tensile elongation experiment.Dog bone-shaped sample characteristics be measuring length be 1.75 inches, gage width be 0.25 inch. Gauge-thickness is determined by extrusion thickness, is about 3.0cm.Each sample is installed on instrument and is tested respectively.Constant deformation speed Rate is 25mm/min.Sample is removed after rupture failure, test is completed.

Table I

Characterize the key value of tested composite tungsten material and stainless steel composite material stress-strain behavior

Shown in Figure 22 during tungsten and the respective tensile elongation of stainless steel composite material are tested at differently strained point Stress value.Make the amount of the stress needed for subject material deformation twice about poor between two kinds of subject materials.As in Table I and Figure 22 as it can be seen that The stress value of composite tungsten material is higher than the value of stainless steel composite material.Although stress value differs 2 times, between stress and strain always Curve and relation are similar.No matter how the composition of particle can obtain viscoplasticity.

The linearly increasing of stress is roughly the same for two kinds of materials between lower yield point to fracture, and difference is 1.5 Within times.The breaking strain % of two kinds of materials is in the range of uncertainty of measurement, about 425 ± 25% strains.Two samples Between the value of difference maximum be elasticity modulus.There are the difference on the order of magnitude for two kinds of storerooms.Although this difference is big, on stretching The rate of deformation that the ASTM guides of modulus measurements are recommended is the 25mm/min used in 1mm/min rather than the experiment.

Figure 23 and 24 is the magnification region of Figure 22.Their data are identical, simply illustrate the initial slope of material and bend Clothes value.

Figure 25 illustrates the viscoplasticity of the THV fluoropolymer materials of the present invention.Data in curve come from following table J.

Table J

Although the stress-strain diagram of polymer is somewhat similar to composite material, it can be seen that the addition of metal enhances Initial modulus simultaneously remains cumulative strain curve and is mutated at the level of reduction.

The performance of stainless steel composite material is tested with characterize each material and with production technology and end article performance It is associated.Composite material is by the IM illustrated above produced and contain 0.5 weight %.The allusion quotation of listed each property is provided for each supplying material Offset.The performance characteristics of the material of supply are tested to characterize each material and related to production technology and end article performance Connection.The representative value of listed each property is provided for each supplying material.Injection moulded embodiment is prepared, material is as follows：

Table K

* IM contains weight 0.5%

* IM contents 0.15%

Being molded performance is：

Table L

Even if the smooth injection of material shows in the material for true VISCOELASTIC FIBER COMPOSITES containing large scale or more than half (with weight Amount or stereometer) in the material of metallic particles form, also available standards extrusion or injection moulding have been thermoformed into the composite material Product.

To confirm not obtaining the influence of true composite characteristics, two kinds of composite materials containing 62 volume % metals are drawn Elongation measurement, a kind of powder of composite material containing interface modification are stretched, and another composite material is free of the powder of interface modification.Two Kind composite material uses ASTM 638-4 type dog bone-shaped sample analysis.By to containing and the composite material without interface modification stainless steel Analysis in collect critical data.

Table M

Composite material does not have useful performance when Figure 26 and 27 shows to be free of IM materials.With 0.4% NZ12 to stainless Steel carries out the tensile property that interface modification changes composite material, the flexible for making material be changed into extending from brittleness packing material True composite material.The breaking strain % of composite material through interface modification is nearly the 100 of the composite material of no interface modifier Times.

Some attached drawings are discussed in detail

Fig. 1 shows the stereogram of the stent of the metal polymer composite comprising the present invention.Stent can be by composite wood The molded tube of material is carved with known machinery or laser method, or stent can be moulded directly as shown form.Stent 10 can include Composite material simultaneously has compliant member 11, and compliant member 11 makes stent expansible when being placed in vessel lumen.Stent has curved Pars convoluta part 13 and linear element 12, it can be by composite material by direct molding technique or by carving the structure by molded tube Formed.

Fig. 2A shows the extrusion part with symmetrical appearance.Extrusion object 20 has 23A containing plug-in unit and symmetrical grooves 24A Main body 21.Such structure 20 is extrudable and be cut into suitable length, and then each length can mate with symmetrical parts, so as to Plug-in unit 23A can be injected in groove 24B while plug-in unit 23B is injected groove 24A, main body 21 and main body 22 is interlocked to be formed and is fixed Mechanically stable component.The component is shown in fig. 2b.Form what is substantially completely filled in whole assembly in Fig. 2A Object.

Fig. 3 shows two kinds of fishhooks 30 and 31.The fishhook includes hook 32,33.Fishing pendant 34,35 is equipped with hook.Fish pendant 34 Pendant is fished for molding, is formed by compression moulding on hook 33.Fish pendant 35 to fish for the press-fit similar to the extrudate of Fig. 2 to fall, including with In the plug-in unit and groove of snap-fit structure.

Fig. 4 shows the construction of two kinds of wheel balancing blocks of the present invention.In Figure 4 A, wheel balancing block 40 includes the present invention Forming blocks 44, forming blocks 44 have can connect balance weight in the adhesive strip 45 on wheel.The balance weight can be with continuous plate Form be extruded and chopped into forming blocks 44, buckled zone 46 is formed before cutting in balance weight 44.The composite material be it is flexible, It is flexible to meet wheel shape shape.Fig. 4 B show the balance weight 41 with composite block 42 and machinery folder 43, machinery folder 43 are configured to be connected to the wheel of haulage vehicle.

Although description above provides feasible disclosure to the composite technology of the present invention, also can be without departing from this hair Bright spirit and scope implement other embodiments of the present invention.Correspondingly, the present invention embodies in subsidiary claims.

Note

The invention further relates to embodiments below.

1. the VISCOELASTIC FIBER COMPOSITES of a kind of metal and polymer, the composite material includes：

(a) metallic particles, its particle diameter cause the particle less than 5 weight % to be less than about 10 microns, the amount of the particle Account for about 45 to about 95 volume % of the composite material；With

(b) polymer phase, the polymer phase account for about 5 to about 55 volume % of the composite material,

Wherein when being subject to deformation force, the VISCOELASTIC FIBER COMPOSITES shows feature stresses-strain curve, the curve tool Have in ε_AThe yield stress maximum A at place, in ε_BThe lower yield stress minimum B at place, in ε_CThe second yield stress maximum at place With fracture starting point C, in ε_D0 strain at place destroys D, the ε of the composite material_DMore than 10%, each ε represents the increase of strain %.

2. according to 1 composite material, wherein the stress point A is higher than 0.2MPa.

3. according to 1 composite material, wherein the stress point B is less than 60MPa.

4. according to 1 composite material, wherein the stress point C is higher than 0.2MPa.

5. according to 1 composite material, wherein the volume filling of the metallic particles is more than 45 volume %.

6. according to 1 composite material, wherein the volume filling of the metallic particles is more than 54 volume %.

7. according to 1 composite material, wherein the polymer is more than 1.3g/cm for density³Polymer containing halogen.

8. according to 1 composite material, wherein the composite material includes about 0.0005 to about 2 weights for accounting for the composite material Measure the interfacial modifier material of %；

9. according to 1 composite material, wherein the composite material includes about 0.0005 to about 1 weight for accounting for the composite material Measure the interfacial modifier material of %；

10. according to 1 composite material, wherein the metallic particles includes the gold with the distribution of about 10 to 70 micron grain sizes Belong to.

11. according to 7 composite material, wherein the metallic particles is about 70 to 250 microns comprising at least 5 weight % particle diameters Metal.

12. according to 4 composite material, wherein the polymer is more than 1.7g/cm comprising density³Fluoropolymer.

13. according to 1 composite material, wherein the excluded volume of the metallic particles is about 20% to about 55 volume % and institute Metal is stated with the amount of about 95-96 weight % to exist.

14. according to 2 composite material, wherein the stress point A is located at about at 1-10MPa.

15. according to 3 composite material, wherein the stress point B is located at about at 1-10MPa.

16. according to 4 composite material, wherein the stress point C is located at about at 1-10MPa.

17. according to 1 composite material, wherein the metallic particles includes at least about 10 weight % at about 70 to 250 microns The particle of the particle of scope and at least 5 weight % in about 250 microns of range above.

18. according to 1 composite material, wherein the polymer is about 1.8g/cm comprising density³Fluoropolymer.

19. according to 1 composite material, wherein the metal includes tungsten.

20. a kind of heat transfer structure, the structure includes：

(a) heat source；

(b) heat transfer layer；With

(c) heated structure；

Wherein described heat transfer layer includes metal and polymer viscoelastic composite material, and the composite material includes metal Grain, polymer phase and interface modifier, the particle diameter of the metallic particles to be less than 5% particle less than about 10 microns, described The amount of particle accounts for about 45 to about 95 volume % of the composite material；The polymer phase accounts for about the 5 of the composite material to about 55 volume %；The interface modifier accounts for about 0.005 to about 2 weight % of the composite material；And the heat transfer layer is led Hot coefficient is greater than about 1W-M^-1°K^-1。

21. according to 20 heat structure, wherein the thermal conductivity factor is about 50 to arrive about 175W-M^-1°K^-1。

22. according to 20 heat structure, wherein the thermal conductivity factor is 75-155W-M^-1°K^-1。

23. according to 20 heat structure, wherein the thermal conductivity factor is about 87-105W-M^-1°K^-1。

24. according to 20 structure, wherein the useful working range of the composition is about -50 DEG C to about+130 DEG C.

25. according to 20 heat structure, wherein the circularity of the metallic particles, which is more than 14, density, is more than 5-21g/cm³。

26. according to 20 heat structure, wherein the composite density is more than 8-12g/cm³。

27. according to 20 heat structure, wherein the polymer is more than 1.7g/cm for density³Polymer containing halogen.

28. according to 20 heat structure, wherein the composite material includes the colouring agent of about 5 weight %.

29. according to 28 heat structure, wherein the colouring agent includes pigment, dyestuff, fluorescent dye or its mixture.

30. according to 20 heat structure, wherein the metallic particles includes the tungsten with the distribution of about 10 to 70 micron grain sizes.

31. according to 20 heat structure, wherein the metallic particles includes tungsten, the tungsten at least 5 weight % particle diameters are about 70 To 250 microns.

32. according to 20 heat structure, wherein the polymer includes fluoropolymer.

33. according to 20 heat structure, wherein the excluded volume of the metallic particles is about 20% to about 55 volume % and institute Metal is stated with the amount of about 70-95 weight % to exist.

34. according to 20 heat structure, wherein the metallic particles includes at least about 10 weight % in about 70 to 250 microns of models The particle of particle and at least 5 weight % in about 250 microns of range above enclosed.

35. according to 20 heat structure, wherein the polymer includes fluoropolymer.

36. according to 20 heat structure, wherein the metal includes tungsten.

37. according to 20 heat structure, wherein the metallic particles includes bismuth, the bismuth at least 5 weight % particle diameters are about 70 To 250 microns.

38. according to 20 heat structure, wherein the metallic particles includes ferrous metal, the ferrous metal at least 5 weight % Particle diameter is about 70 to 250 micrometer ranges.

39. according to 38 heat structure, wherein the metallic particles includes stainless steel.

Claims

(a) metallic particles, 10 microns of metallic particles is more than comprising particle diameter, and the amount of the metallic particles accounts for the composite material 40 to 96 volume %, the particle include the external coating of interface modifier；With

(b) polymer phase, the polymer phase account for 4 to 60 volume % of the composite material,

Wherein described polymer is before the VISCOELASTIC FIBER COMPOSITES is incorporated to, when the polymer is subject to stretching force to break to initial When splitting, feature stresses coping behavior, including upper yield stress, lower yield stress and fracture strength are shown；With

For wherein described VISCOELASTIC FIBER COMPOSITES when being subject to stretching force to initial collapse, the VISCOELASTIC FIBER COMPOSITES displays that spy Stress-strain behavior, including upper yield stress, lower yield stress and fracture strength are levied,

It is less than 10 microns wherein no more than the diameter of the metallic particles of 5 weight %.

2. composite material as claimed in claim 1, wherein when the VISCOELASTIC FIBER COMPOSITES extrude or reprocess again and with After when being subject to stretching force to initial collapse, the VISCOELASTIC FIBER COMPOSITES also shows feature stresses coping behavior, including upper surrender Stress, lower yield stress and fracture strength.

3. the composite material of composite material as claimed in claim 2, wherein reset condition has heat and viscoelastic property and again The identical composite material of machining state has identical heat and viscoelastic property.

4. the VISCOELASTIC FIBER COMPOSITES of a kind of metal and polymer, the composite material includes：

Wherein described polymer is before the VISCOELASTIC FIBER COMPOSITES is incorporated to, when being subject to deformation force to initial collapse, display Feature stresses strain curve, the curve have in ε_AThe yield stress maximum A at place, in ε_BThe lower yield stress minimum at place B, and in ε_CThe second yield stress maximum C at place；With

Wherein described VISCOELASTIC FIBER COMPOSITES shows feature stresses-strain curve when being subject to deformation force to initial collapse, described Curve has in ε_AThe yield stress maximum A at place, in ε_BThe lower yield stress minimum B at place, and in ε_CSecond surrender at place should Power maximum C；

5. the composite material of composite material as claimed in claim 4, wherein reset condition has heat and viscoelastic property and again The identical composite material of machining state has identical heat and viscoelastic property.

6. composite material as described in claim 4 or 5, wherein described in the wrong at the stress point A of the VISCOELASTIC FIBER COMPOSITES Take stress maximum ε_AHigher than 0.2MPa.

7. composite material as claimed in claim 6, wherein the surrender at the stress point A of the VISCOELASTIC FIBER COMPOSITES should Power maximum ε_AFor 1-10MPa.

8. composite material as described in claim 4 or 5, wherein described in the wrong at the stress point B of the VISCOELASTIC FIBER COMPOSITES Take stress minimum ε_BLess than 60MPa.

9. composite material as claimed in claim 8, wherein the surrender at the stress point B of the VISCOELASTIC FIBER COMPOSITES should Power minimum ε_BFor 1-10MPa.

10. composite material as described in claim 4 or 5, wherein described in the wrong at the stress point C of the VISCOELASTIC FIBER COMPOSITES Take stress maximum ε_CHigher than 0.2MPa.

11. composite material as claimed in claim 10, wherein the surrender at the stress point C of the VISCOELASTIC FIBER COMPOSITES Stress maximum ε_CFor 1-10MPa.

12. the composite material as any one of claim 1 to 5, wherein the metallic particles includes iron, tungsten, copper, or its Alloy, or its mixture, and volume filling is more than 54 volume %.

13. the composite material as any one of claim 1 to 5, wherein the polymer is more than 1.3g/cm for density³'s Polymer containing halogen.

14. composite material as claimed in claim 13, wherein the polymer containing halogen is more than 1.7g/cm comprising density³Fluorine Polymer.

15. the composite material as any one of claim 1 to 5, wherein the composite material, which includes, accounts for the composite wood The interfacial modifier material of 0.1 to 1 weight % of material.

16. composite material as claimed in claim 15, wherein the composite material includes and accounts for the 0.1 of the composite material and arrive The interfacial modifier material of 0.5 weight %.

17. the composite material as any one of claim 1 to 5, wherein the metallic particles is comprising micro- with 10 to 70 The metal of rice particle diameter distribution.

18. the composite material as any one of claim 1 to 5, wherein the excluded volume of the metallic particles is 20 bodies Accumulate % to 55 volume % and the metal exists with the amount of 95-96 weight %.

19. the composite material as any one of claim 1 to 5, wherein the composite density is more than 4.36g/cm³。

20. the composite material as any one of claim 1 to 5, wherein when measuring under the same conditions, with the gold Identical composite material of the metal particles without the external coating comprising the interface modifier is compared, on the metallic particles The coating of the interface modifier allows the freedom of motion of bigger between the particle in the polymer phase.

21. composite material as claimed in claim 20, wherein the interface modifier be chemically bonded to the metallic particles and The polymer phase not being chemically bonded in the composite material.

22. the composite material as any one of claim 1 to 5, wherein the interface modifier be chemically bonded to it is described Metallic particles is without the polymer phase that is chemically bonded in the composite material.

23. the composite material as any one of claim 1 to 5, wherein the metallic particles includes zinc.

24. the composite material as any one of claim 1 to 5, wherein the polymer phase includes thermoplastic polymer.

25. a kind of wheel balancing block product, includes the composite material as any one of preceding claims.