CN1768394B - Cable and article design for fire performance and production method - Google Patents

Abstract

A cable (1) comprises a conductor (3), an insulating layer (2) which forms a self-supporting ceramic layer when exposed to elevated temperatures experienced in a fire, and an additional heat transformable layer (4). The additonal layer (4) can be another layer which forms a self-supporting ceramic layer when exposed to fire, or it can act as a sacrificial layer which decomposes at or below the temperature that the insulating layer forms a ceramic. The addition layer can enhance the strength of the layers before during or after the fire, the structural integrity of the insulating layer after the fire, the resistance of the layers to the ingress of water after the fire, or the electrical or thermal resistance of the layers during and after the fire.

Description

The cable and product design and the production method thereof that are used for fire performance

Technical field

The present invention relates to cable and have at least one insulation or the ceramic cambial product of protection metal substrate, and especially, relate to design and manufacturing and their purposes of cable and product.

Background technology

Wish a kind of metal substrate and fireproof product of comprising of design in many cases.For example, when running into fire, need the fire performance cable to continue to operate and provide circuit integrity.In order to satisfy some standards, when the mode with regulation when (for example, 15 minutes, 30 minutes, 60 minutes, 2 hours) is heated to assigned temperature (for example, 650,750,950,1050 ℃) in the time in appointment, cable usually must the holding circuit integrality.In some cases, before the heating period, during and afterwards, cable is carried out conventional mechanical shock.In the later stage of heat cycles or after the heating period, their resist the performance of other factors that may experience in fire for accurate measurement, and they are annotated or spraying by water also often.

In the past by make with glass fibre and can satisfy these requirements for the fire performance cable with the conductor that the belt that mica is handled twines this cable.Twine this conductor at production period with belt, and apply at least one insulating barrier subsequently.Be exposed under the temperature of rising, the exterior insulation degraded layer also separates, but this glass fibre keeps mica to go up in position.Have been found that these belts effective holding circuit integrality in fire, but because extra manufacturing step, produce that their are quite expensive.And the process that belt is wrapped on the cable is relatively slow compared with other cable production stages, therefore twines the integral production that this belt has slowed down cable, has further increased cost.Attempted reducing cost by avoiding using belt and squeeze out the cable coating of being made up of the polymerization composition of softness, this soft polymerization composition forms insulating ceramics, and the continuous circuit property finished is provided in the time of in being exposed to fire.

This pottery formation synthetic is known in the art.For example, US4269753 and US4269757 have described directly pottery have been formed the coatings applications of synthetic in the copper cash of shorter length.When covered wire is exposed to 850 ℃ air in the time of following 30 minutes, this coating forms firm with hard ceramic substrate and without any the crack and can not separate with copper cash.US6387512 has shown when by applying 500 volts of voltages 903 ℃ of heating 2 hours, pottery has been formed coatings applications in electric conductor and holding circuit integrality.International application No.PCT/AU2003/00968 with Pollymers Australia Pty Ltd name discloses the silicone polymer based on pottery formation synthetic that is applicable to cable and other application, and when being heated to high temperature, it forms self-supporting ceramic materials.Still the international application No.PCT/AU2003/01383 with Pollymers Australia Pty Ltd name discloses the self-supporting pottery formation synthetic that is applicable to cable and other application, when being exposed to the high temperature relevant with fire, it presents contraction a little or does not shrink.

Although the pottery of prior art forms synthetic required electricity and/or thermal insulation can be provided in theory, but other physical characteristics that pottery forms synthetic before being exposed to high temperature and afterwards, practical application for these materials, especially in the cable application, very difficult realization takes into account the needs that adapt to less desirable physical properties.Desirable, this pottery form that layer should adapt in fire that the experience temperature raises and fire after during the reduction temperature, mismatch between the hot coefficient of the extension of metal substrate and pottery formation synthetic, before being exposed to high temperature, during and have enough mechanical properties afterwards, the structural intergrity that keeps it, and especially be exposed between the megathermal period and be necessary the watertight composition that provides enough afterwards the time.

Therefore, an object of the present invention is to form material by the pottery on the metal substrate fire performance cable or fire performance product are provided, it has overcome the problem of one or more reality relevant with using pottery formation material.

Summary of the invention

According to an aspect, the invention provides a kind of cable, comprise at least one conductor, when being exposed to high temperature, form ceramic insulating barrier and at least one thermal change layer, the cambial physical characteristic of this insulating ceramics of this layer enhancing when being exposed to high temperature.

The application finds by at least one thermal change layer is provided in addition, by additional thermal change layer can adapt to be exposed between the megathermal period and should the cambial characteristic of pottery afterwards the time in deficiency.When cable is exposed to the high temperature that experiences usually in fire, provide at least one extra play to strengthen the overall permanence of cable.

In preferred structure of the present invention, at least one thermal change layer is compounded on the conductor with this insulating barrier.In the time of in being used in cable design, this at least one thermal change layer can improve, compensates or overcome the problem relevant with this pottery formation material.

This insulating barrier can be formed by various compositions.Preferably, by being exposed to high temperature, the composition that forms pottery during the temperature that namely meets with in the condition of a fire forms this insulating barrier.This pottery forms synthetic can based on silicone polymer, perhaps comprise the basic composition of the mixture with silicone polymer and non-silicone polymer based on non-silicone polymer.This synthetic can comprise the various inorganic compositions that can produce pottery by pyroreaction.This synthetic also can comprise the additional function additive, as fire retardant etc.

Preferably, this insulating barrier is that pottery forms synthetic, and this pottery forms synthetic and be exposed to the temperature formation self-supporting ceramic layer that experiences usually in fire.International application No.PCT/AU2003/00968, its full content in conjunction with as a reference, has been described the fire prevention synthetic at this, and it comprises silicone polymer, based on 5-30wt.% mica and the 0.3-8wt.% glass additive of this synthetic total weight.Preferably, this pottery forms layer and is being exposed between the megathermal period and afterwards the time, appears a little or does not have a change in size.Disclose suitable pottery and form material in above-mentioned international application No.PCT/AU2003/01383, its full content in this combination as a reference.A kind of synthetic has been described in this patent application, and it includes organic polymer, silicate mineral filler and flux or precursor, and this precursor causes the amount of flux to account for the 1-15wt.% of residue as a result.

According to a second aspect of the invention, a kind of method that produces cable is provided, may further comprise the steps: squeeze out the insulating barrier on the conductor, this insulating barrier forms the self-supporting pottery when being exposed to high temperature, with squeeze out at least one auxiliary layer, this auxiliary layer is variable during being exposed to the temperature relevant with fire, to strengthen the cambial physical characteristic of this pottery.Preferably, this at least one auxiliary layer and insulating barrier are compound.

Preferably, the characteristic that strengthens by this auxiliary layer be following one of at least:

I) be exposed to the fire mechanical strength of this combination layer afterwards;

Ii) being exposed to should the cambial structural intergrity of pottery after the fire;

Iii) be exposed to the fire resistance of this combination layer to intaking afterwards;

Iv) during being exposed to fire and afterwards resistance or the thermal resistance of this combination layer.

In other aspects of the present invention, a kind of method that designs cable is provided, may further comprise the steps: select insulating barrier to be used for being squeezed on the conductor, this insulating barrier forms the self-supporting ceramic layer when being exposed to the high temperature that experiences in fire, before being exposed to fire, during and determine the cambial characteristic of this pottery afterwards the time, and select to be used for the material of the second layer, this second layer can strengthen the cambial physical characteristic of this pottery, and should be squeezed on the conductor with at least one auxiliary layer by pottery formation layer.Preferably, this pottery formation layer and at least one auxiliary layer are compounded on this conductor.

Selectable at least one auxiliary layer to strengthen the cambial characteristic of this pottery is:

I) be exposed to the high temperature mechanical strength of this combination layer afterwards;

Should form layer to the maintenance of structural intergrity by pottery after ii) being exposed to high temperature;

Iii) be exposed to the high temperature resistance of this conductor to intaking afterwards;

Iv) during being exposed to fire and afterwards resistance or the thermal resistance of this combination layer.

Although the common reference cable in above-mentioned aspect of the present invention, cable design and cables manufacturing are discussed; but it should be apparent to those skilled in the art that; the present invention can be applied to the design of fire performance product equally; this fire performance product is used for other application; comprise that at this this product metal substrate and at least one protection pottery forms layer or coating, and require this product to be applied to be exposed to during the fire and afterwards.The particular example of the applicable actual conditions of the present invention includes, but are not limited to the strip of paper used for sealing that contacts with metal substrate for fireproof; Slit filler (that is the gummed auxiliary material that, is used for infiltration); Be used for the fire prevention of metallic door, bulkhead, floor and other structures on cabin, train, aircraft, truck and the automobile; Fire barrier in the building, barrier, ceiling and furnace lining; The metal shell that is used for the electronic equipment of building or open air; The steel structure frame that is used for multi-story structure is with insulating frame and allow it to keep required load bearing stength in the time that increases; The coating that is used for architecture pipe; Be used for the combustible material memory block, as the fire barriers of fuel and ammunition depot, oil plant and chemical processing plant; And the protection military vehicle, comprise ship, avoid the influence of burning ammunition.

Therefore, in other aspects of the present invention, comprise the fire performance product, produce the method for fire performance product and the method for design fire performance product.This product comprises metal substrate, forms insulation or protective layer and at least one thermal change layer of pottery when being exposed to high temperature, the physical characteristic when its reinforced insulation or protection pottery formation layer are exposed to high temperature.

When design comprises that at least one pottery forms the cable of layer and metal substrate or fire performance product, for the definite deficiency of said composition in being exposed to fire time of its application, and select one or more thermal change layers to overcome these deficiencies.Therefore, in this application the characteristic of one or more thermal change or auxiliary layer strengthened should the cambial characteristic of pottery.

Use should pottery during being exposed to behind the high temperature this pottery that forms pottery to form a problem that material meets be to be exposed to fire and afterwards the time intensity.

According to a preferred embodiment of the present invention, this at least one thermal change layer is the intensity layer, preferably is compounded in pottery and forms on the layer.In order to be exposed between the megathermal period at least and to provide afterwards the time required strength characteristics, this at least one thermal change layer can comprise that second pottery forms layer.Minimum essential requirement for this layer is that the pottery ratio that it forms passes through insulation or protects pottery formation layer formed pottery harder, and this synthesize ceramic is self-supporting, and it does not suffer significantly to reduce dimensionally when changing pottery into.In cable application, this layer can be used as supplemental dielectric layer or is used as restrictive coating.This second pottery forms layer and preferably includes organic polymer, inorganic filler, and this inorganic filler is mineral silicate and inorganic phosphate preferably.Preferably, the second pottery formation layer also comprises aluminium hydroxide.Preferably, inorganic phosphate is APP.Preferably, this layer not contacting metal conductor or metal substrate to minimize this inorganic phosphate and will influence the insulation characterisitic of this cable or to suffer in the possibility of metal substrate back reaction.

Use is exposed to the material that forms pottery after the high temperature, and for example cable insulation material may run into a problem, i.e. the normal running intensity of this material may be less than the desirable intensity of the application before meeting fire.Therefore, at least one thermal change layer can be manipulation strength layer (that is, having good mechanical property under normal operating condition), preferably, is compounded in this pottery and forms on the layer.Use this cable of these courses to provide the location required strength grade first, and in installation, protect cable, and allow this composite insulation to satisfy required standard.Because the properties of materials that in this manipulation strength layer, uses, in the time of between the megathermal period of in being exposed to fire, experiencing or afterwards, do not need these layers to assist this cable.Form layer if this manipulation strength layer also is second pottery, be exposed between this megathermal period or can providing intensity continuously afterwards the time.As hereinafter described, this manipulation strength layer also can be that glaze forms layer.

Stipulate this second ceramic cambial minimum thickness by the thickness that this conductor and pottery form insulating barrier, by thicker conductor with need be used for the second layer than the insulating barrier of thick-layer with the maintenance structural intergrity.

It is believed that to form this inorganic phosphate in the layer in the decomposition temperature of other synthetics of phosphoric acid or be lower than in the temperature of this decomposition temperature at this second pottery and decompose.Under the situation of APP, ammonia also is catabolite.Phosphoric acid approaches to form in the carbon containing charcoal at organic material any organic material is dewatered, and this carbon containing charcoal becomes pottery in the stage of back, and this moment, ammonia was used for forming required other porosity of level.

The cambial pottery of this preferred second pottery forms synthetic and comprises:

Based on the total weight of synthetic, account for the polymer base synthetic of weight at least 15%, this polymer base synthetic comprises the organic polymer that accounts for weight at least 50%;

Based on the total weight of this synthetic, account for the inorganic phosphate of weight 20-40%, preferably, APP and

Based on the total weight of this synthetic, account for the inorganic refractory filler of weight 15%, preferably the silicate mineral filler.

Second pottery forms layer and also comprises additional inorganic filler or the additive that accounts for weight 10-20%, and it comprises select at least a from the hydroxide of magnesium or aluminium or oxide group.

Preferred additional filler or additive are aluminium hydroxide, preferably account for weight 10-20%.

This second pottery forms layer when measuring temperature in being exposed to fire also needs to form self-supporting and hard porous ceramic (having 20vol% usually to the porosity of 80vol%), and at least 40% is inorganic filler in total composition.

Organic polymer is that a kind of organic polymer that makes is as the polymer of the main chain of this polymer.For example, do not think that silicone polymer is organic polymer; Yet it can be used for mixing with organic polymer is as microcomponent, and when they carry out thermal decomposition, to advantageously provide the silica source (formation of auxiliary ceramic) with finely particulate.This organic polymer can be any kind, for example thermoplastic polymer, thermoplasticity synthetic rubber, cross linkage synthetic rubber or rubber, thermosetting polymer.This organic polymer can the precursor synthetic form exist, this precursor synthetic comprises reagent, prepolymer and/or oligomer, it can react to form the organic polymer of at least a the above-mentioned type jointly.

This organic polymer composition can comprise mixture or the fusions of two or more different organic polymers.

Preferably, this organic polymer can adapt to the required a large amount of inorganic additives of formation pottery, such as APP, aluminium hydroxide and silicate mineral filler, keeps good processing and mechanical property simultaneously.Wish according to the present invention in the fire prevention synthetic, to comprise a large amount of inorganic fillers because when comparing with the synthetic with low filler content, these compositions in being exposed to fire the time loss in weight will reduce.When adding thermal behavior and form pottery, therefore the synthetic that loads APP, aluminium hydroxide and the silicate mineral filler of relative high concentration seldom shrinks and the crack.

For selected organic polymer, during high temperature in being exposed to the condition of a fire, it is favourable can not flowing or melt before its decomposes.Most preferred polymer is included in the fire prevention synthetic and has the polymer of cross linkage after forming, or has thermoplasticity but have high-melting-point and/or be decomposed to form the polymer of pottery near this fusing point the time; Yet, also can use the polymer with these characteristics.Suitable organic polymer can obtain in market, perhaps can or adopt the known technology manufacturing by the application.Provide the example of suitable organic polymer below, but should be understood that by such as the additional composition that in the fire prevention synthetic, comprises, prepare and use the mode of this synthetic, and the use of this synthetic also can influence the selection of concrete organic polymer.

As shown, be used for organic polymer of the present invention and comprise thermoplastic polymer, thermosetting polymer and (thermoplasticity) synthetic rubber.This polymer can comprise polyolefinic homopolymers and copolymer.

This organic polymer that is specially adapted to make cable coating is obtainable thermoplasticity and cross linkage paraffin based on polymer on the market, the copolymer of any density and terpolymer.The cobalt monomer is known for those skilled in the art.Obtainable special additives is to have thermoplasticity and the cross linkage polyethylene that density 890 to 960kg/ rises on the market, copolymer with ethene of acrylic acid, vinyl and other paraffin monomers, ethene, the terpolymer of propylene and diene monomers, so-called thermoplastic vulcanizate, one of them composition is cross linkage, and continuous phase is thermoplastic, and by peroxidating, radiation and so-called silane treatment, the variant of all polymer has thermoplasticity or cross linkage.

This organic polymer that is present in this polymer base composition accounts for weight at least 50%.This helps this polymer base to form the additional composition of loading, and does not damage the processing characteristics of whole synthetic.Should be noted that this polymer base composition can comprise silicone polymer.Yet in this case, the organic polymer that is present in usually in this polymer base composition is compared more important with this silicone polymer.Therefore, in this polymer base was formed, organic polymer can be that 5:1 is to 2:1, for example from 4:1 to 3:1 to the weight ratio of silicone polymer.For percentage by weight, if exist, on the basis of the total weight of the fire prevention synthetic of preparation, the silicone polymer that exists accounts for weight 2 to 15% usually.When using the composition of organic and silicone polymer, the silicone polymer of high concentration can produce handling problem, and should consider this problem when preparing synthetic according to the present invention.

Tending to influences the quantity upper limit that polymer base is formed in the fire prevention synthetic by the ideal characterisitics of synthetic of preparation.If the amount that this polymer base is formed has surpassed 60% of whole synthetic weight, in the condition of a fire, unlikely form viscosity, firm residue.Therefore, this polymer base is formed the weight 15% to 60% that forms the fire prevention synthetic that accounts for preparation usually, and preferably from 20% to 50%.

Synthetic according to this embodiment of the invention comprises that also the silicate mineral filler is as necessary composition.This filler (for example typically comprises aluminosilicate, kaolinite, montmorillonite, pyrophyllite-known clay), alkaline aluminosilicate (for example, mica, feldspar, spodumene, petalite), magnesium silicate (for example talcum) and calcium-silicate (for example, wollastonite).Can use two or more different silicate mineral fillers.This filler is obtainable on the market.In environment of the present invention, silicon dioxide (silica) is not the silicate mineral filler.

The pottery of this second layer forms composition and comprises and account for weight 15%, preferred at least 25% silicate mineral filler.Tend to stipulate by the processing characteristics of this synthetic the maximum of this composition.

Except the mineral silicate filler, can add various other inorganic fillers.Preferred inorganic filler is the hydroxide of magnesium and aluminium or their oxide.

Can also be combined in 1000 ℃ of infusible inorfils, comprise alumina silicate fibre.The mechanical property that this can cause reducing change in size at high temperature and/or improve this synthesize ceramic.

Usually, be exposed to high temperature (to 1000 ℃) afterwards, remaining residue usually constitutes at least 40% of this synthetic proportion of accounting for before the pyrolysis, and preferably at least 55%, preferred at least 70%.Wish the residue of higher quantity, because this can improve this ceramics strength under all temperature.

For during being exposed to fire and improve the cambial resistance of this pottery or thermal resistance afterwards; normal running at cable or product is used (namely; before meeting fire) in; this at least one thermal change layer can be functional layer; itself and the self-supporting ceramic phase ratio that this insulation or protective layer form have formed more weak self-supporting pottery.For example, use the restrictive coating of the type to have in cable design and surpass the benefit of using traditional restrictive coating, because should will increase thickness by the tradition restrictive coating, and thus after this cable is exposed to fire, the electrical insulation characteristics of remaining ceramic coating still keeps.

Pottery being formed synthetic in cable design, to be applied in specific question that metallic conductor produces be to be exposed between the megathermal period and in cooling period subsequently, this metallic conductor will be to expand with the ceramic different speed that forms during heat treated and to shrink.Therefore, even should show good proterties confining force by pottery during forming, the difference in thermal expansion and contraction often causes frangible ceramic crack, and can cause the movement of insulating ceramics coating layer portion, exposes this conductor and damages circuit integrity.At cooling stage, the crack of this ceramic layer is more obvious.Be adhered to this conductive surface when this pottery is strong, or on the oxide layer that this conductive surface forms the time (during meeting fire), this problem is emphasized.For example, according to copper conductor, the difference in the thermal expansion can cause cuprous oxide/cupric oxide surface fracture, and the mobile potsherd that is bonded on the cupric oxide.Though in specific this problem of having described when relating to the metallic conductor that uses in the cable application, but it should be apparent to those skilled in the art that, scribble at metal substrate described type the fire prevention synthetic will produce this problem in any case, because when this synthetic is exposed to high temperature, the different thermal coefficient of expansion of the pottery of metal substrate and formation.The degree of this problem will depend on the extent of pottery and the thermal coefficient of expansion of metal and the intensity of the adhesive of formation from the teeth outwards.

Therefore, in other embodiments of the invention, proposed this problem, namely the mismatch between the thermal coefficient of expansion of metal substrate and ceramic material is protected metal substrate in case meet fire, and ceramic material provides protection to this substrate.

In an embodiment of the present invention, at least one the thermal change layer that provides at this metal substrate is sacrifice layer, the synthetic that forms this layer includes organic polymer and inorganic filler, wherein can this sacrifice layer decompose at high temperature or when being lower than high temperature, cause between substrate and pottery forming this inorganic filler layer, in order to prevent or MIN pottery is adhered on the substrate.

Use this sacrifice layer to guarantee to make the pottery of this metal substrate and formation keep being separated from each other by this layer in this mode, with bottom line or avoid pottery to adhere on the substrate.In fact, this inorganic filler does not adhere on this metal substrate or the pottery at least, thereby reduces pottery during cooling crack and mobile trend, because it has slowed down the stress by the difference generation of the thermal coefficient of expansion between substrate and the pottery.

Remaining this inorganic filler allows the pottery of substrate and formation to expand independently and shrinks after this sacrifice layer decomposes.In cable application, reducing two results that the formation crack produces in the ceramic layer is the exposures that reduced bare exposed conductor, and has reduced the passage of water inlet.Therefore, comprising sacrifice layer in design has strengthened on being exposed to fire or has been exposed in the water because electrical short causes the resistance of fault.In this case, employed this inorganic filler preferably has high resistance, therefore further auxiliary circuit integrality.In all situations, the low-density of residual packing, powdery characteristic are to the favourable barrier that conducts heat that provides, and namely this residual filler is adiabatic.

This sacrifice layer is formed by the synthetic that includes organic polymer and inorganic filler usually.At this, term " organic polymer " comprises the various polymer that satisfy following standard.At first, this organic polymer must be can decompose to stay seldom or do not have solid residue typical the chance under the fiery temperature.The temperature that the pottery of this organic polymer in pottery formation layer forms or this decompose below temperature.The second, this organic polymer must load with the inorganic filler (typically account for weight 25-75% in total the composition, preferably surpass 50%) of appropriate level, keeps good processing properties simultaneously.The processing characteristics of the synthetic of this sacrifice layer is important, if push this synthetic especially usually in cable application.This organic polymer can adapt to the inorganic additive of high-load fully, so that after the hot classification of this sacrifice layer, the pantostrat of the essence of inorganic filler is retained in this substrate surface, this is important.Need this inorganic filler and substrate separation, and form pottery as mentioned above, and if in this organic polymer, exist not enough inorganic additive, this inorganic filler can not realize preventing the directly effect of contact between the pottery of substrate and formation.If this inorganic filler is not to be evenly dispersed in this organic polymer, also same problem can appear.Compare with other application, in application-specific, more can allow the contact of some degree between substrate and the pottery.Cable application need have the pantostrat of inorganic filler between conductor and pottery.

At high temperature this is important to this polymer to this inorganic filler Fails To Respond, because this can produce the product that adheres to this substrate and/or pottery.Suitable organic polymer can obtain on market, perhaps can or adopt known technology to make by the application.Provided the example of operable suitable organic polymer below.

Can from the copolymer of the homopolymers of alkene and one or more alkene, select useful thermoplastic polymer.The particular example of suitable polymers comprises ethene, propylene, butene-1, isobutene, hexene, 1, the homopolymers of 4-methylpentene-1, amylene-1, octane-1, nonylene-1 and decylene-1.Can use these polyolefin of pre-oxidation, Ziegler-Natta or metallocene catalysts, this is being known in the art.Also can use two or more copolymers of these alkene.These alkene also can with other monomeric substances, as vinyl or diolefin compound combined polymerization.The particular example of operable copolymer comprises the copolymer based on ethene, as ethylene-propylene copolymer (for example EPDM), the copolymer of ethene-1-Butylene copolymer, ethene-hexene-1 copolymer and ethene and two or more above-mentioned alkene.

This TPO also can be two or more mixture of above-mentioned homopolymers or copolymer.For example, this mixture can be above-mentioned one or more polypropylene that have, hp-ldpe, high density ethylene, a kind of single-phase mixture in the system of PB Polybutene-1 and the polar monomer that comprises olefin copolymer, wherein, this olefin copolymer is such as ethylene/acrylic acid copolymer, the ethylene/methacrylic acid ester copolymer, ethene/ethyl propylene acid ester copolymer, ethene/butylacrylic acid ester copolymer, ethylene/vinyl base acetate copolymers, ethylene/acrylic acid/ethyl propylene acid esters terpolymer and ethylene/acrylic acid/vinylacetate terpolymer.

Be noted that the selection of this organic polymer will depend in part on the purposes of this synthetic.For example, in application-specific, need the pliability (such as in cable coating) of this synthetic, and when loading this inorganic filler, this organic polymer need be selected according to its characteristic.Have been found that polyethylene and ethylene, propylene synthetic rubber are particularly useful for the synthetic of cable coating.And, selecting this organic polymer should consider that in this polymer unwinds be any harmful or toxic gas that can produce.In application-specific, can allow the generation of this gas.

After this organic polymer decomposes, the coating of this inorganic filler will be retained on the substrate.Be noted that for application-specific (for example, cable), wish a little less than the continuous and mechanicalness of this coating.The function of this inorganic additive is to minimize or prevent at high temperature to form between the substrate and pottery to adhere to.Consider that for this this is important, namely this inorganic filler is nonreactive under the temperature that may meet with in the condition of a fire.Any reaction that comprises this inorganic filler can cause the formation of product, and it has weakened the effect of this inorganic filler.

The inorganic filler of Shi Yonging can be that homogeneity is dispersed in any inorganic material in this organic polymer in this embodiment, and is inertia under the temperature in fire.The use of this inorganic filler is center of the present invention.Use separately organic polymer will can not avoid adhesion between the pottery of substrate and formation as this sacrifice layer.In this case, this polymer will only decompose, and stay seldom or do not stay residue.This pottery causes the problems referred to above with direct and this substrate basis.

Desirable, this inorganic filler has high melting temperature, for example surpasses 1000 ℃, preferably above 1500 ℃.The cost of this additive also may be a factor.The example of suitable inorganic additive comprises metal oxide, metal hydroxides, talcum and clay.Especially, talcum and clay can be used, describedly aluminium oxide, aluminium hydroxide, magnesium oxide, magnesium hydroxide, calcium silicates and zirconia can be formed.The composition of operable two or more inorganic fillers is if be inertia under the temperature of said composition in fire.Preferred, this inorganic filler that uses in this cable is magnesium hydroxide, is favourable because it has low-down conductivity.

This sacrifice layer can comprise one or more additional function compositions, if they do not disturb the effect of this inorganic filler.This supplementary element comprises flame retardant materials and reduces the material of heat and/or conductivity.This sacrifice layer also can be the manipulation strength layer.

This synthetic that is used for this sacrifice layer can assign to prepare by each one-tenth of simple mixing.Can use the mixing arrangement of any routine.If this synthetic has low relatively viscosity, can use dispersing apparatus to handle, the type of for example in paint industry, using.Be full-bodied (higher molecular weight) and can use two rolling mills, internal mixture, Bitruders to wait to handle to the useful material of cable application.If this organic polymer is cross linkage, the polymer of some heating of needs is present in the suitable crosslinking agent.Can use traditional crosslinking agent.

The adaptable specific examples that exceeds the actual conditions of cable application of the embodiment of the invention include, but are not limited to for ferryboat, train and other vehicles fire compartment wall internal layer, fire barrier, barrier, ceiling and internal layer, be used for the coating of architecture pipe; Slit filler (that is the adhesive that, is used for infiltration); Structure fire ［ section keeps its required load bearing stength (or restriction core temperature) to the structural metal framework of this building that insulate to allow at a fixed time ］.

Embodiments of the invention namely are particularly useful in this cable application to the coating of this conductor.Therefore the present invention is applicable to the manufacturing of cable, and this can provide circuit integrity under the situation of catching fire.In the design of this cable, be used for this sacrifice layer and ceramic cambial synthetic and can directly be squeezed in conductor.Can utilize conventional equipment to implement this extruding.Usually the thickness of this sacrifice layer forms 0.2 to 2 millimeter, for example from 0.4 to 1.5 millimeter.The cambial thickness of this pottery will depend on the needs to the particular criteria of the size of conductor and operating voltage.Typically, this insulation thickness will be 0.6 to 3 millimeter.For example, the 35 square millimeters of conductors that are rated for 0.6/1kv for Australian Standard will need about 1.2 millimeters insulation thickness.In non-cable application, sacrifice layer and the cambial suitable thickness of pottery can be determined by experiment test.

In other preferred embodiments of the present invention, at least one thermal change layer is that glaze forms layer, and it also cools off the composition that forms glazed layer after being included in and being exposed to high temperature, and this glazed layer in fact can not permeate water.Provide this glaze to form this insulation or protective layer that the contact of the contiguous also direct physical of layer forms pottery.And find that the glaze that forms can strengthen the intensity of the ceramic layer of structural intergrity and formation after being exposed to high temperature.Therefore, this glaze formation layer also can serve as the manipulation strength layer.In an embodiment of the present invention, unique glaze forms composition and forms glazed layer, and this glazed layer can be blocked in the water that exists on every side.For example, in cable design, this glazed layer is because waterproof and anti-in fact sealing enters conductor.This glazed layer can comprise minor defect, as discontinuous, hole and crack.Preferred content is to allow to become insignificant through the water of this glaze.Preferred this glazed layer is adhesion and continuous, thereby water can not see through this layer.

This glaze forms layer high temperature that is included in the fire and heats the composition that the back cooling can form impermeable barrier.Can natural occurring cooling or as the special measure of extinguishing fire, such as water spray.Can use one or more glazes to form composition.Summarize, can form this glazed layer by softening/fusing, and glaze to form composition coalescent to form continuous and glaze adhesion.By cooling glaze is solidified.According to this explanation, this glaze forms composition and must at high temperature soften/melt, so that single composition particulate can merge to form this glazed layer.Desirable, this glaze forms composition and forms the liquid that has suitable viscosity and can flow (to limited extent), in order to realize the formation of this glazed layer.Although dispensable, form chemical reaction between the composition to the formation of glazed layer negative part responsibility at least at glaze.Can provide other additives, such as the refractory intermixture.

For clear, if forming synthetic, glaze is included in the composition that does not experience necessary coalescent and/or reaction in the temperature relevant with fire, just can not observe this glazed layer effect.Wish that this glaze forms layer and comprises that one or more glazes form composition, it can form suitable glaze under 500 ℃ low temperature.Because this glaze that copper 1080 ℃ of fusings, uses in this cable application forms synthetic and there is no need to be included in " activated " glaze formation composition under the temperature that is higher than this temperature.

Be noted that and wish to form liquid under the temperature of this glaze formation composition in fire.In this temperature, the viscosity of liquid composition is important.If viscosity is too low, it is too fast that this liquid may flow, and can cause the glaze area loss in the specific region, perhaps causes accumulation in other zones.This can cause defective to form.If this glaze conducts electricity and has low viscosity, also can cause the electrical conductivity problems in the cable.For example, when when pottery formation insulating barrier provides this glaze to form layer, the glaze of formation can flow through any hole and/or the crack that exists at this insulating barrier, sets up conducting path from this conductor to the cambial outer surface of this pottery.On the other hand, if liquid is too sticking and at high temperature have high surface tension, can suppress to have suitable moistening and the adhesion of adhesiveness and the formation of continuous glazed layer.When being provided at pottery and forming layer and go up, wish good the soaking and adhere on the ceramic layer that high temperature forms of this glaze.This is for realizing that above-mentioned intensity benefit is important.During heating this liquid glaze of Xing Chenging preferably has low conductivity, low surface tension and the high viscosity of appropriateness at high temperature, and can select this glaze to form composition thus.

Be favourable about the mixture that uses two or more glazes to form compositions.For example, have been found that at high temperature the low melting point composition can be absorbed in the following pottery formation layer relatively.Can mix to reduce this influence by relative low melting point composition is formed composition with the glaze of fusing at high temperature.The mixture that uses glaze to form composition also can increase the temperature range that can form suitable glazed layer.

Consider above-mentioned various factors, can form composition from this glaze of following selection:

A) at high temperature reaction/chemical combination with the compound of two or more materials of forming glass metal.Some prominent examples of this compound comprise silicate (such as mica and feldspar), phosphate, borate and/or their precursor that mixes with basic anhydride, alkaline earth oxide, specific transitions metal oxide (for example, zinc oxide) and/or their precursor." precursor " produces any compound of this material (with compound form) when meaning heating.

B) the at high temperature softening/glass of fusing, the mixture of glass.For cable application, wish that this glass at high temperature has low conductivity.Therefore, this glass preferably has the low alkali composition.

C) composition (a) and (b).

D) have 75% refractory filler, such as, but not limited to, the compound of (c) of aluminium oxide, zirconia, rutile, magnesium oxide and lime.

This is possible, but exhausted dispensable, and namely this glaze formation layer comprises that the mode of this layer as the part of whole design that provide will be provided for supplementary element and this.In one embodiment, this glaze formation layer only comprises the composition that can form this glaze.In this embodiment, in cable design, this composition can be directly applied to this surface of conductors (can be formed layer by this pottery covers) and/or be applied to cover the layer of this conductor, normally the pottery of the cable of Zhi Zaoing forms layer.

Can use this composition by the electrostatic precipitation technology, wherein coated substrate (i.e. this conductor or other cable floors) ground connection and this composition electrostatic charging.Electrostatic force causes that this composition is attracted and accumulates on the surface of this substrate.In fact, the cambial processed continuously part that forms as final cable of using of this glaze of generation.Comprise resin if this glaze forms layer, high output IR lamp or other thermals source can be used for melting this resin, form smooth coating so that it flows.Subsequently, by continuing this heat supply, or can this coating is crosslinked by the UV solidification equipment.In ongoing operation, this can realize during extruded layer is applied in cable.

Glaze forms the quantity of composition and distributes is enough to not make the water infiltration with the glazed layer that allows to form.This particle size, fibre length, length-width ratio or fibre diameter will be influential to it according to the concrete condition of glaze formation composition.When using glaze to form the particulate of composition, average particle size is 200 microns or littler, preferred 50 microns or littler, and preferred 20 microns or littler.This glaze forms synthetic can comprise that the glaze that is dispersed in the suitable carriers forms composition.Can form this synthetic by known hybrid technology.This carrier can make this synthetic be applied on the basic layer uniformly.The important feature of this carrier is that it has the ability that the glaze that loads q.s forms composition, in order at high temperature can form suitable glaze, keeps suitable processing characteristics to allow to use this synthetic simultaneously, for example as the layer of cable.Therefore, this carrier must have satisfied rheological properties.Wish that this carrier also has the ability that the composition that will disperse and the substrate of using glaze formation synthetic soak, and when cooling or sclerosis, develop high strength (characteristic that depends on this carrier).This also is important, and namely this carrier does not comprise any material that at high temperature disturbs glaze to form.Desirable, this carrier is a kind of thermal decomposition under this temperature and do not stay the material of residue.The residue that exists may cause the discontinuous and defective in the glazed layer, and can cause the conductivity problem, if this residue conducts electricity.The heating of preferred this carrier or decomposition can not cause too much gaseous by-product to produce.And preferably this carrier decomposes being lower than under the temperature that this glaze begins to form.

In cable application, this carrier can be thermoplastic polymer, and this polymer is generally used for providing the layer of cable, such as restrictive coating.In this case, this carrier loads the glaze formation composition of appropriate amount and pushes to form glaze in the mode of routine and forms layer.Preferably, this carrier is set for non-adhesive layer is provided as soon as possible, because this glaze formation layer is used as a part that continues processing usually, this lasting processing is included in upward application of glaze formation layer (passing through extruding usually) extra play.If at high temperature this carrier polymer does not dryout only, the application of this specific process is not too useful.

In needing the process of quick-hardening, preferred, this carrier can be hot curing or radiation curing.Therefore, can select this glaze to form the carrier components of composition from alkyl acrylate, alkyl methacrylate, the homopolymers with acrylic double bond low-molecular-weight polyurethanes (being called urethane acrylate) and silicones and copolymer, and then it can be by hardening as the UV radiation of secondary stiffening system after the atmospheric humidity.But the radiation hardening resin that is applicable to other kinds of this carrier components is to have the functional polyester of acrylates.

In cable application, the rheological force that this glaze forms synthetic should make this synthetic be extruded to form smooth and continuous layer by routine techniques.The viscosity of this carrier that uses and glaze and the possible extra composition of formation will be important.Pure mode by explanation, this vector resin may be 25 ℃ of viscosity with 15-1500cP, preferably at 25 ℃ from 30-400cP.

Replace as other, by the latter is contacted with the slurry that glaze in being dispersed in suitable medium forms composition, this glaze formation composition can be provided on the outer surface of this cable.By soaking the pool and brushing and to use this slurry.Preferably, layer is fixing fast to be gone up in place in order to realize this glaze formed, the medium that wherein disperses this glaze to form composition be quick-drying or volatilization.This slurry also can include the organic polymer composition, and it is generally comprised within the aluminosilicate that dissolves in the alkali metal silicate solutions, such as potassium silicate.Add and pine for, this organic polymer forms glass.And, might use sol-gel technique to apply the superficial layer that glass forms synthetic in this embodiment.

This glaze form composition to the weight ratio of carrier/medium usually in the scope of 0.9:1 to 1.2:1.This is important, i.e. high as far as possible this ratio of maintenance and help the formation of continuous glazed layer.

In case use and suitable fixing, common at least one extra play by cable covers this glaze and forms layer.Can use this layer in the downward extruding in position that this glaze formation composition of application takes place.For example, can provide this glaze to form layer with insulating barrier that this conductor directly contacts, and after it is used, form at this glaze at once and layer squeeze out the sheath polymeric layer.Forming layer at this glaze provides one deck can help to go up in place the latter is fixing.Can form between layer and this restrictive coating at this glaze the anti-layer that cuts is provided.This anti-layer that cuts can be extruded on this glaze formation layer, then this restrictive coating is expressed to this anti-cutting on the layer.

Depend on that in this coating composition glaze forms the cut of composition, this glaze forms layer and has 500 microns or littler thickness usually, and preferred 250 microns or littler, preferred 100 microns or littler.In order to save, preferably use glaze to form the minimum (and thickness) of composition thereby the result who realizes wishing, as mentioned above.Typically, this pottery of only being to use of the cambial thickness of this glaze forms the sub-fraction of layer thickness.For example, the cambial thickness of this glaze normally should pottery form layer thickness 50% or littler.In fact, it can be 0.8 millimeter that this pottery forms layer, and this glaze formation layer is 0.4 millimeter thickness.Those skilled in the art can revise these relative thicknesses certainly, thereby optimize the effect of each layer.

The actual suitable glaze that uses of the present invention forms composition, and carrier and medium can obtain on market.

The present invention also provides the manufacture process of cable or fire-proof product by technology described here.

Description of drawings

Fig. 1 is the perspective view that has the cable of pottery formation insulating barrier according to of the present invention;

Fig. 2 is the perspective view of multiconductor cable, and wherein synthetic of the present invention is as sheath;

Fig. 3 has shown the possible design that is used for fire performance product 1; With

Fig. 4 has shown the cross section of position II among Fig. 3.

Embodiment

It is particularly useful when synthetic of the present invention is used for the coating of conductor.Therefore this synthetic is applicable to the manufacturing that the cable of circuit integrity can be provided when catching fire.

Fig. 1 and 2 has shown uniconductor and multiconductor cable 1,10 respectively, and it has insulating barrier 2 or layer 12, and has additional thermal change layer 4,14.In these two kinds of cable design, depend on the effect of this extra play, the position of this insulating barrier and this thermal change layer can exchange.

In the design of this cable, these layers can directly be squeezed on the conductor, and this extra play is squeezed on the insulating barrier.In other words, in multicore cable, they can be used as void filler, as adding in the parts to finish the independent extrusion packing thing of these parts, as the internal layer before using lead or belt sheath.

In fact, this synthetic will typically be squeezed on the surface of conductors.Utilize conventional equipment can implement this extruding in a usual manner.As mentioned above, the thickness of this insulating barrier will depend on the needs to the particular criteria of the size of conductor and operating voltage.Typically, this insulating barrier will have 0.6 to 3 millimeter thickness.For example, being rated for 0.6/1kv35 square millimeter conductor and will needing about 1.2 millimeters insulation thickness for Australian Standard.Be noted that can produce cable and fire performance product so that the thermal change layer of two or more complementations to be provided, it demonstrates at high temperature good heat and electrical insulation characteristics.The present invention can make the cable of graceful simple designs, because do not need to comprise independent manufacturing step, unique layer provides electric insulation, intensity or fire resistance characteristic.This cable can comprise other layers, as anti-layer and/or the restrictive coating of cutting.Yet this cable does not need extra play at high temperature to keep electric insulation.

In Fig. 3 and 4 embodiment that show, this metal substrate 12 has protective finish 16, and it comprises that at least one pottery forms layer 20 and at least one thermal change layer.The example of thermal change layer is sacrifice layer 17, its have glazed layer 18 or form firm ceramic 18 layer or glazed layer 18 and form firm ceramic 19 layer group and.

Illustrate embodiments of the invention in the unrestricted example below.

Example 1

A kind of synthetic forms based on the EP polymer of synthetic A, and this synthetic A comprises as the described APP of this specification and other mineral.Discovery is being exposed to the expansion that has slight (2%) after 1000 ℃.Discovery is compared with other pottery formation synthetics has dense top layer, and is exposed to back waterproof in the fire.With, when utilizing 3 hybrid tests describing in PCT/AU/2003/00183, it has the high strength that exceeds the factor 7.5 than the pottery formation synthetic B that does not comprise APP.

Use the cable that this synthetic makes and the testing time that is used for resistance, but find that the pottery of ratio forms the low factor 10 of resistance of synthetic B.

By only just it utilizes this layer in intensity and the anti-advantage that provides waterborne as the skin on the pottery formation layer of this synthetic B.

Synthetic A

Synthetic B

1.5 the square millimeter conductor is bundled by 7 0.5 millimeter ordinary copper lead and to make, and is insulated by the ceramic composition B of 0.5 millimeter wall thickness.Above the second layer of the synthetic of listing one by one among this synthetic A directly is squeezed in, so that 1.0 millimeters synthetic wall thickness to be provided.This insulated electric conductor is equipped with the same dielectric conductor of three different lengths by distortion.

Insulated electric conductor with twisting superscribes obtainable halogen on the market, low cigarette, hypotoxicity thermoplastic compound then, forms final cable.Then this cable is carried out the circuit integrity test of AS/NZS3013:1995.

This cable is connected to 240 volts of power supplys that form circuit by certain loads, and 2 hours calcining of experience test under 1050 ℃ final temperature, and the water that carried out then 3 minutes is annotated and sprayed.

The cable that synthetic shown in the passing through is as described made can the holding circuit integrality, and satisfies the needs of this test thus.

Only use the insulating material production of synthetic A to compare cable, and experience identical test, find unsafty execution.

Example 2

Three 200 millimeters sections of 35 square millimeters of copper conductors are used to form different cable design prototypes.Extruding synthetic as the check of sacrifice layer is the main a large amount of ethylene propylene rubbers that add aluminium hydroxides of synthetic C(, and comprises peroxide) and synthetic D(to comprise the silicone polymer of peroxide crosslinked for thermoinduction).It forms the synthetic E(silicone polymer/mica/glass fibre/peroxide 73:20:5:2 of ceramic material when at high temperature heating) be the skin of all three prototypes.By simultaneously this synthetic molding being prepared this prototype with being solidificated on the cut cable.This design and layer thickness are presented in the table 1.

Table 1

Then, in smelting furnace all three prototype cables being heated to 1000 ℃ in air carried out 30 minutes.Then they are taken out from smelting furnace, and cool to room temperature, their situations during cooling monitored.

Prototype cable 1, it does not have layer between conductor and pottery formation synthetic, when taking out from smelting furnace, do not show the visible crack on this ceramic layer.Then, this ceramic insulating material crack gradually during cooling, and this cable is cleaved into several sections.

Prototype cable 2C(is according to the present invention), when taking out from smelting furnace, do not show the visible crack on this ceramic layer, and even the cooling 15 minutes after, insulating material crack or loss do not take place.

Prototype cable 2D has this silicone polymer interlayer, have some cracks on every side from smelting furnace, and after cooling 8 minutes, serious crack takes place when taking out, and big section the insulating material at this cable middle part peels off from this conductor.

After test, the inspection directly perceived and trickle of this cable is shown the oxide layer on strong this copper conductor of connection of the ceramic layer in prototype 1.Because the ceramic block of the displacement of adhering at the thin layer of cupric oxide, this conductor and should pottery between thermal expansion mismatch cause the decomposition of this ceramic layer of cooling period, this cupric oxide is peeled off from this conductive surface.For prototype 2C, observe continuous powdery residue.As if this residue can not or engage with this conductor or the reaction of this ceramic insulating material.Therefore effectively prevent between this conductor and this insulating material, forming any joint.In contrast, the interlayer in prototype 2D presents hard and the nature of glass, and engages with conductor and this ceramic layer.

Example 3

The common annealing copper wire conductor of being made by 19 1.67 square millimeters lead is electric insulation, has based on the sacrifice layer of EP polymer with based on the ceramic cambial silicone synthetic rubber of synthetic E for whole 1.2 millimeters wall thickness simultaneously.Similarly cable does not only have this sacrifice layer by making based on the cambial silicone synthetic rubber of pottery.

With these sample roastings to 1000 ℃ the time, find still to keep in both cases the complete coating of this conductor.

Yet as the sample of cooling, because the interaction between different valent cupric oxide, the conductor in not having this sample of sacrifice layer begins to destroy this pottery and forms layer.

In having the sample of sacrifice layer, this can not take place.

Example 4

EP polymer based on synthetic is made as sacrifice layer in high-resistance by 62% magnesium hydroxide.When being exposed to 1000 ℃, wish Mag (OH) ₂Change the MgO powder into, stay not can potteryization powder mass.

The cable sample of being made by this material comprises 35 square millimeters and 1.5 square millimeters of common annealing copper conductors.In up to 1050 ℃ smelting furnace, test, cause Mag (OH) ₂The desirable MgO that changes into, and the powder bed on the conductor is provided in table 3 by synthetic J() outer pottery forms layer and keeps going up in place.Discovery this layer under 1000 ℃ provides the higher electric resistivity that exceeds than other inner layer material coefficients 2.

Example 5

In this sample, the meticulous muscovite with 40 μ m particle mean sizes by the obtainable UV that to have 25 ℃ of following viscosity be 1175cPs sclerosis acrylic resin (TRA-coat15C) on the market that will account for 46 parts of weight and 10 parts of weight and the glass dust with 525 ℃ of softening points " F " (synthetic that provides in table 2) of 44 parts of weight mix to produce uniform homogeneous blend fully and make glaze formation synthetic.Use soft brush that the pottery that this glaze formation synthetic is applied in the J synthetic of cable sample is formed on the layer then, and also be applied on the identical pottery formation sheet of insulation that is of a size of 25 millimeters X15 millimeter X2 millimeters.In air, be that 2 meters/minute conveyer belt uses F-600 lamp (120W/cm, 360 nanometers) to carry out the cambial UV sclerosis of this glaze in speed.One by behind the radiating element, this sample is hardened.The cambial thickness of this glaze is in the scope of 100-600 micron.In Muffle furnace, the sample of coating was calcined 30 minutes in 1000 ℃ then.In visual examination, the sample of this calcining does not have bigger defective/crack.Discovery is in roasting, and this glaze forms layer and forms the continuous Ceramic glaze of layer formation at this pottery.It is waterproof that this glaze forms layer, and this retains by the water droplet on this glaze and surpasses one minute and be not penetrated into this pottery and form and disclose below the layer.

Example 6

The glass dust that substitutes the 9-23 part weight in the glaze formation synthetic of describing in the example 5 above this with Firebrake ZB or boron oxide compound can further improve the impermeability of this glazed layer.

Example 7

In this example, make glaze and form synthetic by the glass dust with 500 ℃ of softening points " G " of the poly aqueous solution (vinyl alcohol) that comprises 90% water of 40 parts of weight and the glass dust with 525 ℃ of softening points " F " that accounts for 30 parts of weight and 30 parts of weight and the synthetic that provides are mixed to produce fully uniform homogeneous blend in table 2.Using soft brush that this glaze is formed the synthetic K(that synthetic is applied in cable sample then provides in table 3) pottery form on the layer.The cambial thickness of this glaze is in the scope of 150-300 micron.In Muffle furnace, the sample of coating was calcined 30 minutes in 1000 ℃ then.In visual examination, the sample of this calcining does not have bigger defective/crack.In roasting, this glaze forms layer and forms the continuous Ceramic glaze of layer formation at this pottery.It is waterproof that this glaze forms layer, and this retains by the water droplet on this glaze and surpasses one minute and be not penetrated into this pottery and form and disclose below the layer.

Example 8

Be that the meticulous muscovite of about 40 μ m substitutes the glass dust " G " that the glaze of describing in the example 7 above this forms 10 parts of weight in the synthetic and can cause glazed layer even and waterproof with having particle mean size.

Example 9

In this example, this glaze forms synthetic and comprise the glass dust " H " (synthetic that provides) with 525 ℃ of softening points in table 2.The pottery that this glass dust is applied to the synthetic K of cable sample by the vibrated bed that cable is pulled through glass dust forms on the layer.In commercial scale, the application's method is perhaps unactual, but final result in essence with coming to the same thing of obtaining by above-mentioned electrostatic precipitation method.Australian Standard AS3013 according to the speed that is included in 2.5 meters to 3 meters distance 12.5l/min is sprayed water calcines the cable sample that applies 2 hours down at 1050 ℃ with the cable sample uncoated, that other are consistent in Gas stove, sprays water afterwards 3 minutes.The cable that discovery applies according to the present invention has shown than not having the cambial relatively better water-resistance of cable of glaze.In fact, the latter is short circuit in 1 minute, has continued the whole 3 minutes water spray period and have the cambial cable of this glaze.Be sure of that this has clearly proved after being exposed to high temperature, this glaze forms layer and infiltrates this pottery and form effect on the layer reducing water.

Table 2

The composition of the glass dust of appointment in the percentage by weight of the oxide of forming

Glass dust	SiO 2	Na 2O	K 2O	TiO 2	P 2O 5	Al 2O 3	CaO	Fe 2O 3	ZnO	V 2O 5	Other
												F	37.7	14.6	10.6	16.0	1.3	1.2	1.0	3.0	-	-	14.5
G	39.2	2.9	2.2	-	-	5.5	5.3	-	36.2	-	8.7
												H	13.5	18.2	10.8	19.3	1.8	-	-	-	-	8.7	7.7

Example 10

In different carrier polymers, use high glass powder F to make synthetic, comprise to harden acrylic Acid UV and EP polymer.These synthetics are as the thin layer (0.2-0.4 millimeter) on the pottery formation synthetic K, and this pottery forms synthetic K and has been compressed on the common annealing copper conductor of 1.5 square millimeters (7/0.5 millimeter bundle).Find that although suitable glazed layer can be provided, the material in this layer causes the unacceptable reduction of the resistance of this pottery insulating material under 1000 ℃, makes them not be suitable for cable application.

Table 3

Claims (42)

1. the cable with fire performance comprises

At least one conductor,

When the high temperature that is exposed to 1000 ℃, form pottery insulating barrier and

At least one additional heat change layer, described at least one additional heat change layer is that second pottery forms layer, described second pottery forms layer and includes organic polymer, silicate mineral filler and inorganic phosphate, and strengthens and form ceramic described insulating barrier be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

2. cable as claimed in claim 1, wherein when being exposed to described high temperature, described insulating barrier forms the self-supporting ceramic layer.

3. as the cable of claim 1 or 2, wherein said second pottery forms layer and extrudes on described conductor with described insulating barrier, and forms the pottery of self-supporting when being exposed to described high temperature.

4. cable as claimed in claim 3 is wherein ceramic firm than what formed by described insulating barrier by the described second pottery formation layer pottery that forms.

5. cable as claimed in claim 1, wherein said inorganic phosphate is APP.

6. cable as claimed in claim 5 wherein based on the described second ceramic cambial total weight, provides described APP in the weight range of 20-40%.

7. cable as claimed in claim 1, wherein said second pottery form layer and also comprise the additional inorganic filler of selecting from the groups that oxide and the hydroxide of magnesium and aluminium constitute.

8. cable as claimed in claim 7, wherein said additional inorganic filler is aluminium hydroxide.

9. cable as claimed in claim 1, wherein said insulating barrier comprise that pottery forms synthetic, and this pottery forms synthetic and contains polymer, and described polymer is no silicon polymer, silicon polymer, the perhaps mix ingredients of silicon polymer and no silicon polymer.

10. cable as claimed in claim 7, wherein said additional inorganic filler is magnesium hydroxide.

11. the cable with fire performance comprises

At least one conductor,

When the high temperature that is exposed to 1000 ℃, form pottery insulating barrier and

At least one additional heat change layer, wherein said conductor is metallic conductor, described at least one additional heat change layer is arranged on the sacrifice layer on the described metallic conductor, wherein said sacrifice layer is to be formed by the synthetic that includes organic polymer and inorganic filler, and strengthens and to form ceramic described insulating barrier be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer,

Wherein said sacrifice layer comprises the inorganic filler of at least 50% weight, and

Wherein the organic polymer in described sacrifice layer when being exposed to described high temperature, form the pottery described insulating barrier form the pottery temperature in or decompose below the described temperature.

12. as the cable of claim 11, the thickness of wherein said sacrifice layer is the 0.2-2 millimeter.

13. the cable with fire performance comprises

At least one conductor,

When the high temperature that is exposed to 1000 ℃, form pottery insulating barrier and

At least one additional heat change layer, described at least one additional heat change layer is that glaze forms layer, after it is included in and is exposed to described high temperature, cooling is to form the composition of glazed layer, described glazed layer is fluid-tight, and strengthens and to form ceramic described insulating barrier be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

14. as the cable of claim 13, wherein said glaze forms layer and comprises that two or more glazes form composition.

15. the cable as claim 13, the cambial composition of wherein said glaze is selected from the group of the composition that comprises two or more materials, and these materials react when described high temperature or make up to form melten glass or the glass of softening or fusing under described high temperature.

16. the cable as claim 13, wherein constitute the cambial composition of described glaze and comprise that glaze forms composition and carrier components, wherein said carrier components can make described glaze form layer and be expressed into jointly on the described conductor at the described layer that forms pottery under the described high temperature.

17. as the cable of claim 16, wherein said glaze form composition to the weight ratio of carrier components at 0.9:1 in the scope of 1.2:1.

18. the cable with fire performance comprises

At least one conductor,

When the high temperature that is exposed to 1000 ℃, form pottery insulating barrier and

At least one additional heat change layer, described at least one additional heat change layer is restrictive coating, with the self-supporting ceramic phase ratio that is formed by described insulating barrier, described restrictive coating forms more weak self-supporting pottery in described high temperature, and strengthens and to form ceramic described insulating barrier be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

19. method of producing cable, comprise insulating barrier is extruded step on conductor, described insulating barrier forms the self-supporting pottery when the high temperature that is exposed to 1000 ℃, and be changed to second pottery of self-supporting when extruding in the temperature that is exposed to 1000 ℃ and have at least one auxiliary layer of varying strength with the described self-supporting pottery that is formed by described insulating barrier, to strengthen the physical characteristic of the described insulating barrier that forms the self-supporting pottery, wherein said at least one auxiliary layer comprises that second pottery forms layer, described second pottery forms layer and includes organic polymer, silicate mineral filler and inorganic phosphate, the described physical characteristic that wherein is enhanced be selected from following one of at least:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

20. as the method for claim 19, wherein said second pottery forms layer pottery that forms when being exposed to described high temperature ceramic firmer than what formed by described insulating barrier.

21. as the method for claim 19, wherein said inorganic phosphate is APP.

22. as the method for claim 21, wherein said APP accounts for the 20-40% of the second ceramic cambial total weight.

23. as the method for claim 19, wherein said second pottery forms layer and also comprise the additional filler of selecting from the group that oxide and the hydroxide of magnesium and aluminium constitute.

24. as the method for claim 23, wherein said additional filler is aluminium hydroxide.

25. as the method for claim 23, wherein said additional filler is magnesium hydroxide.

26. method of producing cable, comprise insulating barrier is extruded step on conductor, described insulating barrier forms the self-supporting pottery when the high temperature that is exposed to 1000 ℃, and at least one auxiliary layer that changes when extruding in the temperature that is exposed to 1000 ℃, to strengthen the physical characteristic of the described insulating barrier that forms the self-supporting pottery, wherein said at least one auxiliary layer is that glaze forms layer, it is after being exposed to described high temperature, cooling to be forming fluid-tight glazed layer, the described physical characteristic that wherein is enhanced be selected from following one of at least:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

27. as the method for claim 26, wherein said glaze forms layer and comprises that at least one glaze forms composition and carrier components, described at least one glaze form composition to the weight ratio of carrier components in the scope of 0.9:1 to 1.2:1.

28. refractory product; comprise metal substrate; when the high temperature that is exposed to 1000 ℃, form the protective layer of pottery; with at least one thermal change layer; described at least one thermal change layer is that second pottery forms layer; described second pottery forms layer and includes organic polymer, silicate mineral filler and inorganic phosphate, and strengthens and form ceramic described protective layer be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

29. as the product of claim 28, wherein said second pottery forms layer and form the ceramic firm pottery that produces than the described layer that forms pottery under described high temperature.

30. as the product of claim 28, wherein said inorganic phosphate is APP.

31. as the product of claim 30, wherein based on the described second ceramic cambial gross weight, in the scope of 20-40% weight, provide described APP.

32. as the product of claim 28, wherein said second pottery forms layer and also comprise the additional filler of selecting from the group that oxide and the hydroxide of magnesium and aluminium constitute.

33. as the product of claim 32, wherein said additional filler is aluminium hydroxide.

34. refractory product; comprise metal substrate; when the high temperature that is exposed to 1000 ℃, form the protective layer of pottery; with at least one thermal change layer; described at least one thermal change layer is arranged on the sacrifice layer on the described metal substrate; wherein said sacrifice layer is to be formed by the synthetic that includes organic polymer and inorganic filler, and strengthens and to form ceramic described protective layer be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer,

Wherein at described high temperature or be lower than under this high temperature, described sacrifice layer decomposes, and causes forming the inorganic filler layer between metal substrate and pottery, be adhered on the substrate in order to prevent or minimize described pottery, and

Wherein said sacrifice layer comprises the inorganic filler of at least 50% weight.

35. refractory product; comprise metal substrate; when the high temperature that is exposed to 1000 ℃, form the protective layer of pottery; with at least one thermal change layer; described at least one thermal change layer is that glaze forms layer, and after it was included in and is exposed to described high temperature, cooling was to form the composition of glazed layer; described glazed layer is fluid-tight, and strengthens and to form ceramic described protective layer be selected from following physical characteristic one of at least when the high temperature that is exposed to 1000 ℃:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

36. the product as claim 35, the cambial composition of wherein said glaze is selected from the group of the composition that comprises two or more materials, and these materials react when described high temperature or make up to form melten glass or the glass of softening or fusing under described high temperature.

37. as the product of claim 35, wherein constitute the cambial synthetic of described glaze and also comprise carrier components, it can make described glaze form layer is applied to form pottery under described high temperature described layer.

38. method of producing refractory product, comprise that the layer that will form pottery under 1000 ℃ high temperature is applied in the step on the metal substrate, described pottery forms layer and form the self-supporting pottery when being exposed to described high temperature, with the step of using at least one auxiliary layer, described at least one auxiliary layer comprises that second pottery forms layer, described second pottery forms layer and includes organic polymer, silicate mineral filler and inorganic phosphate, and when described auxiliary layer is exposed to described high temperature, change, form layer and be selected from following physical characteristic one of at least to strengthen described pottery:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

39. as the method for claim 38, it is ceramic firmer than what produced by the described layer that forms pottery under described high temperature wherein to form layer pottery that forms by second pottery under described high temperature.

40. as the method for claim 38, wherein said inorganic phosphate is APP.

41. as the method for claim 40, wherein based on the described second ceramic cambial gross weight, in the scope of 20-40% weight, provide described APP.

42. method of producing refractory product, comprise that the layer that will form pottery under 1000 ℃ high temperature is applied in the step on the metal substrate, described pottery forms layer and form the self-supporting pottery when being exposed to described high temperature, with the step of using at least one auxiliary layer, described at least one auxiliary layer is that glaze forms layer, it is after being exposed to described high temperature, cooling is to form glazed layer, described glazed layer is fluid-tight, and when described auxiliary layer is exposed to described high temperature, change, form layer and be selected from following physical characteristic one of at least to strengthen described pottery:

(i) be exposed to the fire mechanical strength of combination layer afterwards;

(ii) be exposed to fire ceramic cambial structural intergrity afterwards;

(iii) be exposed to the fire resistance of combination layer to intaking afterwards;

(iv) during being exposed to fire and afterwards resistance or the thermal resistance of combination layer.

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