CN102534297A - Alloy material with thermal expansion coefficient in gradient change and preparation method thereof - Google Patents
Alloy material with thermal expansion coefficient in gradient change and preparation method thereof Download PDFInfo
- Publication number
- CN102534297A CN102534297A CN2010106080497A CN201010608049A CN102534297A CN 102534297 A CN102534297 A CN 102534297A CN 2010106080497 A CN2010106080497 A CN 2010106080497A CN 201010608049 A CN201010608049 A CN 201010608049A CN 102534297 A CN102534297 A CN 102534297A
- Authority
- CN
- China
- Prior art keywords
- alloy
- thermal expansivity
- gradient
- powder
- changes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to an alloy material with a thermal expansion coefficient in a gradient change and a preparation method of the alloy material. The alloy material comprises a substrate material component and a thermal expansion coefficient adjusting phase component, wherein the substrate material component is one or a mixture of several elements of Cu, Ni, Cr, Mn, Co and Fe in an optional ratio; the thermal expansion coefficient adjusting phase component is one or a mixture of several fibers of W, Mo, Al2O3, SiC and Si in an optional ratio; a gradient transition alloy is at least divided into two sections; and the distribution of the components of a thermal expansion coefficient adjusting phase in each section of the alloy changes in a gradient way. The method disclosed by the invention is suitable for preparing gradient transition alloy bars and pipes, the thermal expansion coefficient of the prepared alloy material changes in the gradient way, and the alloy material is well matched with welded ceramics and metals. The gradient transition alloy has important significance to release residual stresses generated in a ceramic and metal connecting process.
Description
Technical field
The present invention relates to alloy material that a kind of thermal expansivity changes in gradient and preparation method thereof.
Background technology
Stupalith has high vacuum resistance to air loss, high thermal conductivity, high-wearing feature, low-steam pressure more, and performances such as good thermostability and chemicalstability.Therefore, stupalith has widespread use in fields such as vacuum electronic, Aeronautics and Astronautics.But stupalith has shortcomings such as bad plasticity, cold-forming property difference equally, does not generally use separately, but often combines with metallic substance, with the form use of linker.
In pottery and metal sealing process, one of gordian technique that needs solution is the alleviation of stress of sealing.Because pottery differs bigger with the physicochemical property of metallic substance, especially thermal expansivity differs bigger, and it is very big directly to cause both to connect stress, even causes connection failure.Thermal expansivity between by the transition layer between weldering pottery and the metal be alleviate stress of sealing the most directly, effective means; But when being differed greatly with the thermal expansion metal coefficient by the weldering pottery, individual layer or double-deck transition layer have been not enough to eliminate the destruction of stress of sealing to the closure performance by self viscous deformation.In addition, transition layer uses and cause the loss on the performance itself also can for too much whole web member.Therefore, prepare a kind of thermal expansivity between by weldering pottery and metal, and the alloy material that thermal expansivity changes in gradient is to alleviating pottery and metal sealing stress, it is significant to improve the sealing-in quality.
Summary of the invention
One of the object of the invention is the alloy material (hereinafter to be referred as the gradient transition alloy) that provides a kind of thermal expansivity to change in gradient for pottery and metal sealing.The composition profiles design of thermal expansivity adjusting phase and corresponding gradient transition alloy pipe synoptic diagram are shown in Fig. 1-a, Fig. 1-b in the gradient transition alloy; Actual constituent after the vacuum sintering distributes as shown in Figure 2, and variation of gradient transition alloy thermal expansivity and corresponding gradient transition alloy pipe synoptic diagram are shown in Fig. 3-a, Fig. 3-b.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
The alloy material that a kind of thermal expansivity changes in gradient (gradient transition alloy material); Comprise that matrix material constituents and thermal expansivity regulate phase component, said matrix material constituents is one or more the mixing of arbitrary proportion among Cu, Ni, Cr, Mn, Co, the Fe; It is W, Mo, Al that said thermal expansivity is regulated phase component
2O
3, one or more the mixing of arbitrary proportion among the SiC, Si fiber; The gradient transition alloy is divided into two sections at least, and the composition profiles that said thermal expansivity is regulated in every section of alloy changes in gradient.
A kind of optimal technical scheme is characterized in that: the composition profiles that said thermal expansivity is regulated in every section of alloy is respectively 90vol%, 60vol% and 25vol% or 75vol%, 60vol% and 35vol%.
Another object of the present invention is the preparation method that the alloy material that a kind of thermal expansivity changes in gradient is provided for pottery and metal sealing.At first, according to the thermal expansivity size and the gap of and metal ceramic by weldering, design gradient transition alloy base material constituent element, thermal expansivity adjusting reach thermal expansivity mutually and regulate the Gradient distribution in alloy.Then, produce the substrate alloy powder with melting, aerosolization technology.Simultaneously, select for use high-purity, ultra-fine thermal expansivity to regulate phase, itself and alloy base material powder are mixed by design mix.At last, accomplish the preparation of gradient transition alloy through mold pressing global formation, blank vacuum sintering and later stage hot isostatic pressing densification process.This technology is suitable for gradient transition alloy bar material and preparation of pipes, and the thermal expansivity of the alloy material that makes changes in gradient, and all has better matching property with and metal ceramic by weldering.This gradient transition alloy is significant to alleviating the unrelieved stress that produces in pottery and the metal connection procedure.
The present invention adopts powder metallurgical technique, through the graded of control thermal expansivity adjusting composition profiles in alloy, reaches the graded of alloy thermal expansivity.Prepared alloy material will have following characteristic: at first, the thermal expansivity of alloy itself changes in gradient.Secondly, can design the base material of this alloy and regulate mutually and the percentage composition of graded according to actual request for utilization, thereby this alloy has and is welded all matched coefficient of thermal expansion of pottery and metal with thermal expansivity.This technology is fit to preparation gradient transition alloy bar material and tubing.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
The preparation method of the alloy material that a kind of thermal expansivity changes in gradient may further comprise the steps:
(1) gradient transition alloy compositions design
According to thermal expansivity ceramic by weldering and metal, design the body material of forming the gradient transition alloy and regulate mutually, and the content that the thermal expansivity adjusting changes in alloy in gradient designs with thermal expansivity;
(2) gradient transition alloy base material preparation
(1) composition design result set by step takes by weighing the metal of the composition gradient transition alloy substrate of corresponding weight, under protection of inert gas, alloy pig is processed in several kinds of Metal Meltings, uses the aerosolization method with the alloy pig powder by atomization then;
(3) thermal expansivity is regulated mutually and is prepared
Thermal expansivity is regulated and is adopted lower metal of thermal expansivity or ceramic powder mutually, requires to select for use narrow diameter distribution, high-purity, superfine powder;
(4) batch mixing
Press each segment components proportioning of gradient transition alloy designs, take by weighing corresponding transition alloy base material and regulate mutually, each section powder mix is mixed with the high energy ball mill mode respectively with thermal expansivity;
(5) die mould
The die mould of graded alloy adopts compression-moulding methods; Each section powder mix that mixes is injected mould successively, the integral die moulding, when filling with substance requires whenever to pack into before a kind of powder mix of composition; Try one's best installed powder ram-jolt before, and will especially control the add-on of every kind of powder mix;
(6) vacuum sintering
Adopt vacuum sintering technology, the molded blank of gradient transition alloy is carried out sintering processes;
(7) densification sintering
Alloy after the pre-burning is carried out hip treatment, obtain the alloy material that thermal expansivity changes in gradient.
A kind of optimized technical scheme is characterized in that: in the step (1), the component of described body material is one or more the mixing of arbitrary proportion among Cu, Ni, Cr, Mn, Co, the Fe.The component that described thermal expansivity is regulated phase is W, Mo, Al
2O
3, one or more the mixing of arbitrary proportion among the SiC, Si fiber.
In said step (1), according to by weldering pottery and thermal expansion metal coefficient magnitude and gap, design thermal expansivity and regulate percentage composition in transition alloy present position, adopt volume percent, also available quality per-cent more.With the segmentation of gradient transition alloy; It is different that every section thermal expansivity is regulated phase content; But require each other variation tendency in gradient, as from 75vol%, to 60vol%; Arrive the variation tendency of 35vol% again, the thermal expansivity of the gradient transition alloy of preparation will possess from the characteristic of alloy end to end graded thus.Simultaneously,, reach the thermal expansivity and the ceramic phase coupling of alloy one end, the other end thermal expansivity and quilt weldering metallographic phase coupling through thermal expansivity in the alloy being regulated the content control of phase.In addition; When the design alloying constituent; Also require the moity of alloy base material not have big solid solubility mutually, regulate phase otherwise can lose a part of thermal expansivity, thereby destroy the characteristic of alloy thermal expansivity graded with selected thermal expansivity adjusting.
A kind of optimized technical scheme; It is characterized in that: in the step (2); The rare gas element that when the melting of gradient transition alloy base material and later stage aerosolization powder process, adopts is high-purity or technical grade argon gas, helium or nitrogen; The purity requirement of gas is superior to 99.99%, and gaseous tension is controlled at about 1 normal atmosphere during alloy melting.The granularity of gradient transition alloy substrate material be controlled at-300 orders and more than.
A kind of optimized technical scheme is characterized in that: in the step (3), the powder purity that thermal expansivity is regulated phase reaches 99.99%, and granularity is 400～1000nm.
A kind of optimized technical scheme is characterized in that: in the step (4), all more than reaching in 48 hours, mixed powder does not have phenomenons such as reunion, white point to the mixing time of said each section mixed powder.
A kind of optimized technical scheme is characterized in that: in the step (5), when injecting mould, regulate the order that the content of phase reduces gradually or increase gradually according to thermal expansivity and inject each section powder mix that mixes, integral die moulding then successively.
A kind of optimized technical scheme is characterized in that: in the step (6), during said vacuum sintering, vacuum tightness is 10
-2～10
-3Pa, sintering temperature and time decide according to gradient transition alloy base material composition, and for example the temperature of vacuum sintering is in 800～1350 ℃ of scopes, and the density of the gradient transition alloy behind the sintering reaches more than 85%.
A kind of optimized technical scheme; It is characterized in that: in the step (7); The atmosphere that said hip treatment is used is superior to 99.99% high-purity argon gas, nitrogen or helium as purity; Hip temperature is decided according to the design mix of gradient transition alloy base material, and for example TR is designed to 700～1200 ℃, and gradient transition alloy density reaches 100% behind the sintering.
One of characteristics of the present invention are that the one-tenth of gradient transition alloy in the said step (1) is grouped into.The gradient transition alloy is regulated phase composite by base material and thermal expansivity, and it is W, Mo or the Al with relatively low thermel expansion coefficient mutually that thermal expansivity is regulated
2O
3Deng material,, realize the graded of transition alloy thermal expansivity through the graded that thermal expansivity is regulated composition in alloy.Gradient transition design of alloy and actual distribution such as Fig. 1-a and Fig. 1-b and shown in Figure 2, gradient transition alloy thermal expansivity graded synoptic diagram is shown in Fig. 3-a and Fig. 3-b.
Two of characteristics of the present invention are in the said step (2), adopt powder metallurgical technique to prepare the matrix powder of gradient transition alloy.In the step (2) with several kinds of metals of composition gradient transition alloy substrate material before this through melting, process alloy, alloy powder is produced in atomizing again, rather than uses the direct mechanical powder mix of several kinds of metal powders forming body material.Alloy powder is compared with the mechanically mixing powder, and composition profiles is more even.In addition, also controlling composition profiles and the design mix of thermal expansivity adjusting in the matrix powder more easily more presses close to.
Three of characteristics of the present invention are in the said step (3) that thermal expansivity is regulated and selected narrow size distribution, high-purity, superfine powder mutually for use.Powder purity is superior to 99.99%, and granularity is the ultrafine powder of 400～1000nm.
Four of characteristics of the present invention are in said step (4), (5), (6), adopt mixed powder, pressed compact, agglomerating powder metallurgical technique to prepare the gradient transition alloy.After thermal expansivity being regulated the different mixed powder of phase content and being injected mould successively, the influence of factor such as Elements Diffusion must make the different powder contact interface of composition proportion thicken when receiving powder to flow, be pressed into suffered external force of blank and sintering.That is to say; The distribution that thermal expansivity is regulated in the gradient transition alloy after the vacuum sintering is being not that kind that designed originally; There is tangible composition abrupt interface; Present tangible graded trend, but the variation tendency of composition gradual change, the distribution of its design mix and actual constituent such as Fig. 1-a and Fig. 1-b and shown in Figure 2.Therefore, the thermal expansivity of gradient transition alloy also is the variation tendency that increases (or reducing gradually) gradually.In addition, mix powder, pressed compact, agglomerating preparation technology and only be fit to gradient transition alloy bar material and preparation of pipes.
Five of characteristics of the present invention also are in the said step (7), for improving gradient transition alloy density, the gradient transition alloy after the vacuum sintering have been carried out hip treatment again.
Advantage of the present invention is:
(1) the transition alloy material that changes in gradient of thermal expansivity; The thermal expansivity of himself from alloy one end to the other end direction; Present gradually the variation tendency that increases (or reducing gradually), and the thermal expansivity at two ends welds pottery and metallographic phase coupling with quilt respectively.This alloy can effectively be alleviated pottery and metal solder stress, improves welding quality.
(2) can be according to the coefficient of thermal expansion mismatch situation of and metal ceramic by weldering, body material, the thermal expansivity of design composition gradient transition alloy are regulated and are reached the composition profiles that thermal expansivity is regulated phase mutually.When being differed by weldering pottery and thermal expansion metal coefficient hour, can the transition alloy be divided into two sections, every section thermal expansivity is regulated the phase content difference.When being differed big by weldering pottery and thermal expansion metal coefficient, can with the transition alloy be divided into three sections and more than, the content of thermal expansivity adjusting phase changes in gradient between every section.
(3) adopt this alloy of powder metallurgic method preparation; The thermal expansivity that can realize alloy is gradually the variation tendency that increases (or reducing gradually); Rather than the composition sudden change, and then the sudden change of thermal expansivity, because the sudden change of any thermal expansivity all still can cause concentrating of welding heat stress.
(4) adopt the gradient transition alloy of heat and other static pressuring processes preparation to have very high-compactness, resistance to air loss own is good, can satisfy the request for utilization of vacuum electronic industry to material.
Through accompanying drawing and embodiment the present invention is further specified below, but and do not mean that restriction protection domain of the present invention.
Description of drawings
Fig. 1-a, Fig. 1-b are composition profiles design and the corresponding gradient transition alloy pipe synoptic diagram that thermal expansivity is regulated phase in the gradient transition alloy.
Fig. 2 is the actual constituent distribution schematic diagram that thermal expansivity is regulated phase in the gradient transition alloy.
Fig. 3-a, Fig. 3-b are that gradient transition alloy thermal expansivity changes and corresponding gradient transition alloy pipe synoptic diagram.
Fig. 4-a, Fig. 4-b are composition profiles design and the corresponding gradient transition alloy pipe synoptic diagram that thermal expansivity is regulated phase in embodiment 1 alloy.
Fig. 5-a, Fig. 5-b are embodiment 1 interalloy composition actual distribution situation and corresponding gradient transition alloy pipe synoptic diagram.
Fig. 6-a, Fig. 6-b are embodiment 1 alloy thermal expansivity variation tendency and corresponding gradient transition alloy pipe synoptic diagram.
Embodiment
The gradient transition alloy of this prepared is used for alumina-ceramic and stainless welding as the stress relieve layer.Wherein, the thermal expansivity of aluminum oxide is 5.5 * 10
-6, stainless thermal expansivity>=16.0 * 10
-6
(1) gradient transition alloy compositions design
According to alumina-ceramic and stainless thermal expansivity size and gap, it is Cu, Ni, the Cr ternary alloy of main body that the gradient transition alloy base material is set at copper, and the quality proportioning is decided to be 90: 8: 2, and wherein the thermal expansivity of Cu is about 17 * 10
-6The thermal expansivity of gradient transition alloy is regulated and is adopted high-purity, ultra-fine Mo powder mutually, and the thermal expansivity of Mo is 5.53 * 10
-6In addition, the composition of gradient transition alloy is divided into three sections, first section volume percent that contains Mo is made as 90vol%, and middle one section Mo content is made as 60vol%, and latter end Mo content is made as 25vol%.Thus, the thermal expansivity of the gradient transition alloy of preparation will be 6～15 * 10
-6Between be gradually the variation tendency that increases.
(2) gradient transition alloy base material preparation
Preparation 1kg gradient transition alloy base material powder is prepared in experiment.At first, (1) composition designs set by step, takes by weighing Cu, Ni and the Cr of corresponding weight.Use the Medium frequency induction melting technology, its melting is alloy pig, require in the fusion process to use argon shield, the purity requirement of gas is superior to 99.99%, and gaseous tension is controlled at about 1 normal atmosphere during alloy melting.With the aerosolization flouring technology alloy pig is sprayed into the Cu-Ni-Cr alloy powder of granularity about-300 orders at last.Wherein, the gas that aerosolization is adopted is high-purity argon gas, and the purity requirement of gas is superior to 99.99%.
(3) thermal expansivity is regulated mutually and is prepared
Be used for thermal expansivity and regulate the Mo metal-powder of phase, the particle diameter of its 80% powder particle is at 400nm～700nm, and Mo powder purity is 99.99%.
(4) batch mixing
(1) described alloying constituent is divided into three sections set by step, and Mo content is respectively 90vol% in every section alloy, 60vol% and 25vol%.The Cu-Ni-Cr alloy powder and the Mo powder of corresponding proportioning are mixed, mixed respectively 48 hours with the mixed powder of high energy ball mill then, phenomenons such as the not reunion of mixed powder, white point three kinds of heterogeneity proportionings.
(5) die mould
With three kinds of powder that mix set by step (1) said order be respectively charged into mould, the powder that a kind of powder mix of whenever packing into all will be tried one's best and put into before the ram-jolt, integral die moulding then.Mold shape adopts cylindrical, and pressure is used 200MPa.
(6) vacuum sintering
With the gradient transition alloy billet of compression molding, 800～950 ℃ of following vacuum sinterings.Vacuum tightness is 10
-2～10
-3Pa, soaking time is 3 hours.The density of the gradient transition alloy behind the sintering reaches more than 85%.
(7) densification sintering
Gradient transition alloy to after the vacuum sintering carries out hip treatment, and treatment temp is 700～800 ℃, and soaking time is 1.5 hours, and pressure is 150Mpa, and the atmosphere of using is superior to 99.99% high pure nitrogen as purity.Gradient transition alloy density reaches 100% behind the sintering.
(8) gradient transition alloy practical application
Cylindrical gradient transition alloy is processed into pipe, dimensional requirement and Al
2O
3Pottery and stainless steel are complementary, and length is got 1.0cm.Wherein, in the 1.0cm length range, the composition of alloy should comprise those three kinds of step (1) design.
Fig. 4-a, Fig. 4-b are composition profiles design and the corresponding gradient transition alloy pipe synoptic diagram that thermal expansivity is regulated phase in the present embodiment alloy; Fig. 5-a, Fig. 5-b are present embodiment interalloy composition actual distribution situation and corresponding gradient transition alloy pipe synoptic diagram, and Fig. 6-a, Fig. 6-b are present embodiment alloy thermal expansivity variation tendency and corresponding gradient transition alloy pipe synoptic diagram.
Gradient transition alloy pipe is assemblied in Al
2O
3Between pottery and the stainless steel, require to contain alloy one end and the Al of 90vol%Mo
2O
3The pottery assembling contains alloy one end and the stainless steel assembling of 25vol%Mo.The Ag-Cu-Ti solder sheet is placed transition alloy and Al respectively
2O
3And stainless contact interface.At 900 ℃, insulation 5min, vacuum tightness is superior to 5 * 10
-3Under the Pa condition, realize Al with vacuum brazing furnace
2O
3Ceramic and stainless welding.
(9) closure performance test
The experimental result demonstration, behind the gradient transition alloy of employing the present invention preparation, Al
2O
3The leak rate of pottery and stainless steel weld interface reaches 10
-10Pam
3/ s, the sealing-in resistance to air loss when obviously being superior to making transition layer with niobium alloy satisfies the resistance to air loss requirement of electrovacuum field to device fully.
Embodiment 2
The gradient transition alloy of this prepared is used for the welding of C/SiC composite ceramics and TC4 titanium alloy as the stress relieve layer.Wherein, the thermal expansivity of C/SiC composite ceramics is 3.5 * 10
-6, the thermal expansivity of TC4 titanium alloy is 9.7 * 10
-6
(1) gradient transition alloy compositions design
According to the thermal expansivity of C/SiC composite ceramics and TC4 titanium alloy and by weldering pottery and metal self component, the gradient transition alloy base material is set at Ni, two kinds of constituent elements of Fe, composition proportion is decided to be 1: 1.Thermal expansivity is regulated and is adopted high-purity, ultra-fine W powder mutually, and its thermal expansivity is 4.4 * 10
-6Simultaneously, the transition alloying constituent is divided into two sections, the volume percent that contains W in first section alloy is made as 90vol%, and the W content in second section alloy is made as 55vol%.Thus, the thermal expansivity of the gradient transition alloy of preparation will be 4.5～8.0 * 10
-6Between be gradually the variation tendency that increases.
(2) gradient transition alloy base material preparation
Preparation 1kg gradient transition alloy base material powder is prepared in experiment.At first, (1) composition designs set by step, takes by weighing the Fe and the Ni of corresponding weight.Use the Medium frequency induction melting technology then, it is smelted into alloy pig, require in the fusion process to use argon shield, the purity requirement of gas is superior to 99.99%, and gaseous tension is controlled at about 1 normal atmosphere during alloy melting.With the aerosolization flouring technology alloy pig is sprayed into granularity at-300 purpose Ni-Fe alloy powders at last, wherein, the gas that aerosolization is adopted is argon gas, and the purity requirement of gas is superior to 99.99%.
(3) thermal expansivity is regulated mutually and is prepared
Be used for thermal expansivity and regulate the W metal-powder of phase, the particle diameter of its 80% powder particle is at 400nm～700nm, and W powder purity is 99.99%.
(4) batch mixing
(1) described alloying constituent is divided into two sections set by step, and W content is respectively 90vol% in every section alloy, 55vol%.The Ni-Fe alloy powder and the W powder of corresponding proportioning are mixed, mixed respectively 48 hours with the mixed powder of high energy ball mill then two kinds of heterogeneity proportionings.Phenomenons such as the not reunion of mixed powder, white point.
(5) die mould
With two kinds of powder that mix set by step (1) said order be respectively charged into mould, the powder that a kind of powder mix of whenever packing into all will be tried one's best and put into before the ram-jolt, integral die moulding then.Because by weldering C/SiC and titanium alloy is columnar structured, so the mould employing is cylindrical, and alloy is shaped as cylindrical after the mold pressing.Molding pressure is 200MPa.
(6) vacuum sintering
With the gradient transition alloy billet of compression molding, 1250～1350 ℃ of following vacuum sinterings.Vacuum tightness is 10
-2～10
-3Pa, soaking time is 3 hours.The density of the gradient transition alloy behind the sintering reaches more than 85%.
(7) densification sintering
Gradient transition alloy to after the vacuum sintering carries out hip treatment, and treatment temp is 1200 ℃, and soaking time is 3 hours, and pressure is 200Mpa, and the atmosphere of using is superior to 99.99% high-purity argon gas as purity.Gradient transition alloy density reaches 100% behind the sintering.
(8) gradient transition alloy practical application
Cylindrical gradient transition alloy is processed into pipe, and dimensional requirement and C/SiC composite ceramics are complementary, and length is got 1.0cm.Wherein, in the 1.0cm length range, the composition of alloy should comprise those two kinds of step (1) design.
Gradient transition alloy pipe is assemblied between C/SiC and the titanium alloy, and alloy one end that requires to contain 90vol%W contacts with C/SiC, and alloy one end that contains 55vol%W is near titanium alloy.The Cu-Al-Si-Ti solder sheet is placed the contact interface of transition alloy and C/SiC and titanium alloy respectively.At 1060 ℃, insulation 5min, vacuum tightness is superior to 5 * 10
-3Under the Pa condition, realize the welding of C/SiC and titanium alloy with vacuum brazing furnace.
(9) closure performance test
Experimental result shows that during with direct soldering C/SiC of Cu-Al-Si-Ti scolder and titanium alloy, there is obvious crack at the interface, directly causes measuring the vacuum-tightness of closure.And adopt the gradient transition alloy of the present invention's design, preparation, the weld interface place of C/SiC and titanium alloy does not have defectives such as micro-crack, and closure can to bear 2Mpa air pressure air tight.
The gradient transition alloy of this prepared is used for C/C matrix material and stainless welding as the stress relieve layer.Wherein, the thermal expansivity of C/C matrix material is 3.5 * 10
-6, stainless thermal expansivity>=16.0 * 10
-6
(1) gradient transition alloy compositions design
According to C/C matrix material and stainless thermal expansivity size and gap; It is Cu, Ni, the Cr ternary alloy of main body that the gradient transition alloy base material is set at copper; The quality proportioning is decided to be 90: 8: 2, selects this system alloy to be because the thermal expansivity of Cu matrix is 17 * 10
-6, approaching with the stainless steel hot coefficient of expansion.The coefficient of expansion of graded alloy is regulated and is adopted SiC powder and W powder mutually.Wherein, the thermal expansivity of SiC powder is 4.3 * 10
-6, the thermal expansivity of W powder is 4.4 * 10
-6The composition of gradient transition alloy is divided into four sections, and first section volume percent that contains W is made as 50vol%, and the volume percent of SiC is made as 35vol%; Second section volume percent that contains W is made as 40vol%, and the volume percent of SiC is made as 20vol%, and the 3rd section volume percent that contains W is made as 20vol%; The volume percent of SiC is made as 5vol%; The 4th section thermal expansivity regulated mutually and only used the W powder, and without the SiC powder, wherein the volume percent of W powder is made as 8vol%.Thus, the thermal expansivity of the gradient transition alloy of preparation will be 5～16 * 10
-6Between be gradually the variation tendency that increases.
(2) gradient transition alloy base material preparation
Preparation 1kg gradient transition alloy base material powder is prepared in experiment.At first, (1) composition designs set by step, takes by weighing Cu, Ni and the Cr of corresponding weight.Use the Medium frequency induction melting technology, its melting is alloy pig, require in the fusion process to use argon shield, the purity requirement of gas is superior to 99.99%, and gaseous tension is controlled at about 1 normal atmosphere during alloy melting.With the aerosolization flouring technology alloy pig is sprayed into the Cu-Ni-Cr alloy powder of granularity about-300 orders at last.Wherein, the gas that aerosolization is adopted is high-purity argon gas, and the purity requirement of gas is superior to 99.99%.
(3) thermal expansivity is regulated mutually and is prepared
Be used for thermal expansivity and regulate particle diameter that phase SiC powder and W powder purity all reaches 99.99%, 80% powder particle at 400nm～700nm.
(4) batch mixing
(1) described alloying constituent is divided into four sections set by step; The Cu-Ni-Cr alloy powder of corresponding proportioning is mixed with W powder and SiC powder; Mixed 48 hours phenomenons such as the not reunion of mixed powder, white point then respectively with the mixed powder of high energy ball mill with four kinds of heterogeneity proportionings.
(5) die mould
With four kinds of powder that mix set by step (1) said order be respectively charged into mould, the powder that a kind of powder mix of whenever packing into all will be tried one's best and put into before the ram-jolt, integral die moulding then.Mold shape adopts cylindrical, and pressure is used 200MPa.
(6) vacuum sintering
With the gradient transition alloy billet of compression molding, 800～950 ℃ of following vacuum sinterings.Vacuum tightness is 10
-2～10
-3Pa, soaking time is 3 hours.The density of the gradient transition alloy behind the sintering reaches more than 85%.
(7) densification sintering
Gradient transition alloy to after the vacuum sintering carries out hip treatment, and treatment temp is 700～800 ℃, and soaking time is 1.5 hours, and pressure is 150Mpa, and the atmosphere of using is superior to 99.99% high pure nitrogen as purity.Gradient transition alloy density reaches 100% behind the sintering.
(8) gradient transition alloy practical application
Cylindrical gradient transition alloy is processed into pipe, and dimensional requirement and C/C matrix material and stainless steel are complementary, and length is got 1.0cm.Wherein, in the 1.0cm length range, the composition of alloy should comprise those four kinds of step (1) design.
Gradient transition alloy pipe is assemblied between C/C matrix material and the stainless steel, and requiring to contain W is 50vol%, and containing SiC is alloy one end and the assembling of C/C matrix material of 35vol%, and containing W is alloy one end and the stainless steel assembling of 8vol%.The Ag-Cu-Ti solder sheet is placed transition alloy and C/C matrix material and transition alloy and stainless contact interface respectively.At 900 ℃, insulation 5min, vacuum tightness is superior to 5 * 10
-3Under the Pa condition, realize C/C and stainless active method welding with vacuum brazing furnace.
(9) closure performance test
Experimental result shows that behind the gradient transition alloy of employing the present invention preparation, the leak rate of C/C and stainless steel weld interface reaches 10
-10Pam
3/ s satisfies the resistance to air loss requirement of electrovacuum field to vacuum device.
Gradient transition alloy material of the present invention has following purposes: by the characteristic that the thermal expansivity of material own changes in gradient, the stress relieve transition layer when mainly being connected with metal as pottery.In addition, this alloy material has the metallic substance general characteristic, also can be used as structural part and directly uses.
Claims (10)
1. alloy material that thermal expansivity changes in gradient comprises that matrix material constituents and thermal expansivity regulate phase component, and said matrix material constituents is one or more the mixing of arbitrary proportion among Cu, Ni, Cr, Mn, Co, the Fe; It is W, Mo, Al that said thermal expansivity is regulated phase component
2O
3, one or more the mixing of arbitrary proportion among the SiC, Si fiber; The gradient transition alloy is divided into two sections at least, and the composition profiles that said thermal expansivity is regulated in every section of alloy changes in gradient.
2. the alloy material that thermal expansivity according to claim 1 changes in gradient is characterized in that: the composition profiles that said thermal expansivity is regulated in every section of alloy is respectively 75vol%, 60vol% and 35vol%.
3. the preparation method of the alloy material that changes in gradient of a thermal expansivity may further comprise the steps:
(1) gradient transition alloy compositions design
According to thermal expansivity ceramic by weldering and metal, design the body material of forming the gradient transition alloy and regulate mutually, and the content that the thermal expansivity adjusting changes in alloy in gradient designs with thermal expansivity;
(2) gradient transition alloy base material preparation
(1) composition design result set by step takes by weighing the metal of the composition gradient transition alloy substrate of corresponding weight, under protection of inert gas, alloy pig is processed in several kinds of Metal Meltings, uses the aerosolization method with the alloy pig powder by atomization then;
(3) thermal expansivity is regulated mutually and is prepared
Thermal expansivity is regulated and is adopted lower metal of thermal expansivity or ceramic powder mutually;
(4) batch mixing
Press each segment components proportioning of gradient transition alloy designs, take by weighing corresponding transition alloy base material and regulate mutually, each section powder mix is mixed with the high energy ball mill mode respectively with thermal expansivity;
(5) die mould
The die mould of graded alloy adopts compression-moulding methods, and each section powder mix that mixes is injected mould successively, the integral die moulding, and before the powder mix of a kind of composition of whenever packing into, installed powder ram-jolt before;
(6) vacuum sintering
Adopt vacuum sintering technology, the molded blank of gradient transition alloy is carried out sintering processes;
(7) densification sintering
Alloy after the pre-burning is carried out hip treatment, obtain the alloy material that thermal expansivity changes in gradient.
4. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient; It is characterized in that: in the step (1), the component of described body material is one or more the mixing of arbitrary proportion among Cu, Ni, Cr, Mn, Co, the Fe; The component that described thermal expansivity is regulated phase is W, Mo, Al
2O
3, one or more the mixing of arbitrary proportion among the SiC, Si fiber.
5. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient; It is characterized in that: in the step (2); The rare gas element that when the melting of gradient transition alloy base material and later stage aerosolization powder process, adopts is high-purity or technical grade argon gas, helium or nitrogen; The purity of gas is superior to 99.99%, and gaseous tension is controlled at 1 normal atmosphere during alloy melting; Granularity during powder process be controlled at-300 orders and more than.
6. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient is characterized in that: in the step (3), the powder purity that thermal expansivity is regulated phase reaches 99.99%, and granularity is 400～1000nm.
7. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient is characterized in that: in the step (4), the mixing time of said each section mixed powder all more than reaching in 48 hours.
8. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient; It is characterized in that: in the step (5); When injecting mould; Regulate the order that the content of phase reduces gradually or increase gradually according to thermal expansivity and inject each section powder mix that mixes, integral die moulding then successively.
9. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient is characterized in that: in the step (6), during said vacuum sintering, vacuum tightness is 10
-2～10
-3Pa, sintering temperature and time decide according to gradient transition alloy base material composition, and the density of the gradient transition alloy behind the sintering reaches more than 85%.
10. the preparation method of the alloy material that thermal expansivity according to claim 3 changes in gradient; It is characterized in that: in the step (7); The atmosphere that said hip treatment is used is superior to 99.99% high-purity argon gas, nitrogen or helium as purity; Hip temperature is decided according to the design mix of gradient transition alloy base material, and gradient transition alloy density reaches 100% behind the sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106080497A CN102534297A (en) | 2010-12-16 | 2010-12-16 | Alloy material with thermal expansion coefficient in gradient change and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106080497A CN102534297A (en) | 2010-12-16 | 2010-12-16 | Alloy material with thermal expansion coefficient in gradient change and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102534297A true CN102534297A (en) | 2012-07-04 |
Family
ID=46342316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106080497A Pending CN102534297A (en) | 2010-12-16 | 2010-12-16 | Alloy material with thermal expansion coefficient in gradient change and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102534297A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744413A (en) * | 2012-08-01 | 2012-10-24 | 陕西斯瑞工业有限责任公司 | Preparation method of copper-chromium alloy powder and preparation method of copper-chromium alloy pig |
| CN103382534A (en) * | 2013-06-18 | 2013-11-06 | 武汉理工大学 | W-Cu-SiC ternary composite material and preparation method thereof |
| CN104046823A (en) * | 2014-06-13 | 2014-09-17 | 上海和辉光电有限公司 | Graded metal-ceramic composite and preparation method thereof |
| CN104388806A (en) * | 2014-10-21 | 2015-03-04 | 常熟市金成模具有限公司 | Anti-abrasive metal ceramic mould material |
| WO2016141872A1 (en) * | 2015-03-09 | 2016-09-15 | 中南大学 | Method for removing prior particle boundary and hole defect of powder metallurgy high-temperature alloy |
| CN108340094A (en) * | 2017-01-23 | 2018-07-31 | 北京有色金属与稀土应用研究所 | A kind of Ag-Cu-In-Sn-Ti solder alloys and preparation method |
| CN108746637A (en) * | 2018-06-26 | 2018-11-06 | 中南大学 | Aluminium silicon/aluminium silicon carbide gradient composites and preparation method thereof |
| CN109317864A (en) * | 2018-12-06 | 2019-02-12 | 衢州学院 | A kind of preparation method and applications technique of nickel base powder brazing material |
| CN109746455A (en) * | 2019-03-19 | 2019-05-14 | 湖南恒基粉末科技有限责任公司 | A kind of cupric kovar alloy and preparation method thereof |
| CN110438386A (en) * | 2019-09-20 | 2019-11-12 | 南方科技大学 | A kind of Preparation method and use of high-entropy alloy solder |
| CN114889245A (en) * | 2022-04-16 | 2022-08-12 | 上海殷菲合金材料有限公司 | Composite metal sheet and preparation method and application thereof |
| CN115180930A (en) * | 2022-07-05 | 2022-10-14 | 洛阳科威钨钼有限公司 | Powder for transition layer, preparation method and high-temperature-resistant refractory metal matrix protective layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528714A (en) * | 2003-10-16 | 2004-09-15 | 上海交通大学 | Carbon, ceramic-nonmetallic material and metal material connection method |
| CN101143397A (en) * | 2007-11-06 | 2008-03-19 | 北京有色金属研究总院 | C/C and C/SiC composite material and metal connecting method |
| JP2008522370A (en) * | 2004-11-30 | 2008-06-26 | ザ、リージェンツ、オブ、ザ、ユニバーシティ、オブ、カリフォルニア | Sealed joint structure for electrochemical devices |
| CN101734941A (en) * | 2008-11-20 | 2010-06-16 | 北京有色金属研究总院 | Vacuum active brazing process for C/C or C/SiC composite material and metal |
-
2010
- 2010-12-16 CN CN2010106080497A patent/CN102534297A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528714A (en) * | 2003-10-16 | 2004-09-15 | 上海交通大学 | Carbon, ceramic-nonmetallic material and metal material connection method |
| JP2008522370A (en) * | 2004-11-30 | 2008-06-26 | ザ、リージェンツ、オブ、ザ、ユニバーシティ、オブ、カリフォルニア | Sealed joint structure for electrochemical devices |
| US20080268323A1 (en) * | 2004-11-30 | 2008-10-30 | Tucker Michael C | Sealed Joint Structure for Electrochemical Device |
| CN101143397A (en) * | 2007-11-06 | 2008-03-19 | 北京有色金属研究总院 | C/C and C/SiC composite material and metal connecting method |
| CN101734941A (en) * | 2008-11-20 | 2010-06-16 | 北京有色金属研究总院 | Vacuum active brazing process for C/C or C/SiC composite material and metal |
Non-Patent Citations (3)
| Title |
|---|
| 刘彬彬 等: "W-Cu梯度功能材料的热物理性能", 《中国有色金属学报》, vol. 19, no. 3, 31 March 2009 (2009-03-31) * |
| 王瑾: "Al2O3/ Cu 梯度复合材料的制备及磨损性能研究", 《重庆工学院学报》, vol. 20, no. 5, 31 May 2006 (2006-05-31) * |
| 解念锁: "SiCp/Ni 梯度复合材料的制备与热震性能研究", 《山西工学院学报》, vol. 19, no. 1, 31 March 2003 (2003-03-31) * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744413A (en) * | 2012-08-01 | 2012-10-24 | 陕西斯瑞工业有限责任公司 | Preparation method of copper-chromium alloy powder and preparation method of copper-chromium alloy pig |
| CN103382534A (en) * | 2013-06-18 | 2013-11-06 | 武汉理工大学 | W-Cu-SiC ternary composite material and preparation method thereof |
| CN103382534B (en) * | 2013-06-18 | 2016-03-09 | 武汉理工大学 | W-Cu-SiC ternary composite material and preparation method thereof |
| CN104046823A (en) * | 2014-06-13 | 2014-09-17 | 上海和辉光电有限公司 | Graded metal-ceramic composite and preparation method thereof |
| CN104388806A (en) * | 2014-10-21 | 2015-03-04 | 常熟市金成模具有限公司 | Anti-abrasive metal ceramic mould material |
| WO2016141872A1 (en) * | 2015-03-09 | 2016-09-15 | 中南大学 | Method for removing prior particle boundary and hole defect of powder metallurgy high-temperature alloy |
| CN108340094B (en) * | 2017-01-23 | 2020-11-17 | 北京有色金属与稀土应用研究所 | Ag-Cu-In-Sn-Ti alloy solder and preparation method and application thereof |
| CN108340094A (en) * | 2017-01-23 | 2018-07-31 | 北京有色金属与稀土应用研究所 | A kind of Ag-Cu-In-Sn-Ti solder alloys and preparation method |
| CN108746637B (en) * | 2018-06-26 | 2021-01-08 | 中南大学 | Aluminum silicon/aluminum silicon carbide gradient composite material and preparation method thereof |
| CN108746637A (en) * | 2018-06-26 | 2018-11-06 | 中南大学 | Aluminium silicon/aluminium silicon carbide gradient composites and preparation method thereof |
| CN109317864A (en) * | 2018-12-06 | 2019-02-12 | 衢州学院 | A kind of preparation method and applications technique of nickel base powder brazing material |
| CN109746455A (en) * | 2019-03-19 | 2019-05-14 | 湖南恒基粉末科技有限责任公司 | A kind of cupric kovar alloy and preparation method thereof |
| CN110438386A (en) * | 2019-09-20 | 2019-11-12 | 南方科技大学 | A kind of Preparation method and use of high-entropy alloy solder |
| CN110438386B (en) * | 2019-09-20 | 2021-09-28 | 南方科技大学 | Preparation method and application of high-entropy alloy brazing filler metal |
| CN114889245A (en) * | 2022-04-16 | 2022-08-12 | 上海殷菲合金材料有限公司 | Composite metal sheet and preparation method and application thereof |
| CN115180930A (en) * | 2022-07-05 | 2022-10-14 | 洛阳科威钨钼有限公司 | Powder for transition layer, preparation method and high-temperature-resistant refractory metal matrix protective layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102534297A (en) | Alloy material with thermal expansion coefficient in gradient change and preparation method thereof | |
| CN110257679B (en) | Preparation method of molybdenum-based alloy coating | |
| CN105714209B (en) | A kind of 3D printing ceramic on metal mutually strengthens the preparation method of alloy tool powdered steel | |
| CN100537802C (en) | A kind of method for preparing high dense TiAl-base alloy | |
| CN107052350B (en) | A method of connection tungsten material and copper material | |
| CN100478467C (en) | Activated sintering preparation method of fine crystalline non-magnetic wolfram-copper alloy | |
| CN109778042B (en) | High-strength tungsten-based alloy and preparation method thereof | |
| CN110144508B (en) | Two-stage powder metallurgy preparation method of tungsten/steel bimetal collar material | |
| CN102407408A (en) | Welding joint suitable for welding dissimilar metal materials and preparation method thereof | |
| CN107999756B (en) | Method for preparing high-temperature alloy honeycomb heat insulation plate based on injection molding | |
| CN114525438B (en) | Tungsten copper composite material and preparation method thereof | |
| CN103480846A (en) | Connecting method for sintering/welding titanium-steel dissimilar metal | |
| CN105018768A (en) | High-performance copper chromium contactor material and preparing method thereof | |
| CN102179502A (en) | Device and method for preparing metal matrix composite by adopting high-pressure gas to assist infiltration | |
| CN106903307A (en) | A kind of method for preparing powder metallurgy of coform co-sintering tungsten alloy/steel composite material | |
| CN105063394A (en) | Titanium or titanium alloy material preparing method | |
| CN111778424A (en) | Preparation method of effectively controllable skeleton with multi-polar-hole structure | |
| CN112062588A (en) | Metal solid phase diffusion connection method, ceramic connecting piece manufactured by metal solid phase diffusion connection method and application of ceramic connecting piece | |
| CN111438365A (en) | Silver-graphite electrical contact material and preparation method thereof | |
| CN101224496B (en) | Manufacture method of sputtering targets | |
| CN106086513B (en) | A kind of electrovacuum copper molybdenum alloy and preparation method thereof | |
| CN102814499B (en) | Method for quickly preparing precious metal parts at low temperature | |
| AU2020101497A4 (en) | Molybdenum-based alloy coating and substrate having the alloy coating | |
| CN114892064A (en) | FeCrCuVCo high-entropy alloy and preparation method thereof | |
| CN101429607B (en) | Special particle reinforced high-temperature alloy and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120704 |