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CN109396446A - A kind of multistage hole composite material filtering body and preparation method thereof - Google Patents

A kind of multistage hole composite material filtering body and preparation method thereof Download PDF

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Publication number
CN109396446A
CN109396446A CN201811385921.9A CN201811385921A CN109396446A CN 109396446 A CN109396446 A CN 109396446A CN 201811385921 A CN201811385921 A CN 201811385921A CN 109396446 A CN109396446 A CN 109396446A
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powder
sic
particles
filter body
porous composite
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CN109396446B (en
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崔洪芝
魏娜
李振奎
王欢欢
徐瑞琪
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Shandong University of Science and Technology
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Shandong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1103—Making porous workpieces or articles with particular physical characteristics
    • B22F3/1109—Inhomogenous pore distribution
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/12—Intermetallic matrix material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1208—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1216—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Filtering Materials (AREA)

Abstract

本发明公开了一种多级孔复合材料过滤体及其制备方法，它是以不同粒径的Fe粉、Si粉、Al粉、Ti粉、SiCw粉、B4C粉为原料，采用分层模压成型方法压制成自下而上，混合原料颗粒尺度依次增大的圆坯体，每层圆坯体的的厚度自下而上下也是逐渐增大的，然后将压制成型的圆坯体进行分段无压烧结，从而形成自下而上，孔径逐渐越大的不同多级孔径的过滤体。本发明多孔材料以Fe3(Si1‑x,Alx)作为基体包围SiCw、B4C颗粒，形成致密的骨架，且在骨架表面形成Al2O3保护膜，耐腐蚀、抗氧化性、耐摩擦；同时因为骨架中存在SiCw、B4C等陶瓷相，又提高强度、减小线胀系数，从而降低再生加热应力。

The invention discloses a multi-level porous composite material filter body and a preparation method thereof. The filter body uses Fe powder, Si powder, Al powder, Ti powder, SiC w powder and B 4 C powder with different particle sizes as raw materials. The layer molding method is pressed into a round blank with a bottom-up, mixed raw material particle size increasing in turn, and the thickness of each layer of the round blank is also gradually increased from bottom to top. Staged pressureless sintering to form bottom-up filter bodies with different multi-stage pore sizes with gradually larger pore sizes. The porous material of the present invention uses Fe 3 (Si 1-x , Al x ) as a matrix to surround SiC w and B 4 C particles to form a dense skeleton, and an Al 2 O 3 protective film is formed on the surface of the skeleton, which is resistant to corrosion and oxidation. , friction resistance; at the same time, due to the existence of ceramic phases such as SiC w and B 4 C in the skeleton, the strength is increased and the linear expansion coefficient is reduced, thereby reducing the regeneration heating stress.

Description

A kind of multistage hole composite material filtering body and preparation method thereof
Technical field
It is especially a kind of that there is multi-stage porous the present invention relates to a kind of aperture and distribution controllable filtering body and its preparation process The intermetallic compound of structure/ceramic composite filtering body and preparation method thereof.Invention filtering preparation process is simple, former Expect it is from a wealth of sources, it is low in cost, be suitable for automobile, chemical industry, metallurgy industry tail gas, effluent purifying filter assemblies, photo-thermal seawater is light The supporter etc. of change.Belong to materials synthesis and manufacture field.
Background technique
Filtering body is the important component and vapour that mixed gas or liquid are separated, are classified, purify and are enriched with Vehicle, chemical industry, metallurgy industry tail gas, effluent purifying, reduce the critical component of pollution, it is desirable that filter material has high anti-corrosion Property, wearability and heat resistance, while but also with high permeability and enough intensity.Common inorganic material filtering body can be divided into Ceramics, two class of metal.Such as:
United States Patent (USP) US2011097259A1 has invented a kind of ceramic foam with porosity gradient, has axial direction and diameter To porosity gradient.
China Patent Publication No. CN1287048A has invented a kind of gradient ceramic-film tube and preparation method thereof, the ceramic-film tube Fenestra aperture be from inside to outside in the gradient distribution continuously enlarged.
China Patent Publication No. CN1532170A has invented a kind of preparation method of gradient porous ceramic filter element, this method It is to mix varigrained ceramic powder with high temperature bond agent solution respectively, the mist projection granulating after ball milling, in ceramic powder body surface Bread covers one layer of high temperature adhesives, forms varigrained orthopaedics particle, then by orthopaedics particle respectively with formed bond, increase Hole agent, water are mixed to form blank, and blank is distributed into respectively in different mold layers by different grain size, then deviate from mold layer, Isostatic pressing, drying, finally by green body high temperature sintering.
China Patent Publication No. CN1623627A has invented a kind of filtering material and preparation method thereof of gradient distribution, the mistake Filter material material is the filtering body for the gradient distribution that the aperture of presenting from top to bottom of building of several fibers reduces, it is this from top to bottom Gradient consecutive variations can selectively be collected by the particle in filtering fluid, improved and received dirty space, reduce filtration resistance.
China Patent Publication No. CN101564621A has invented a kind of gradient pore structured titanium filter core and preparation method thereof, should Method by titanium valve, hydride powder, sodium chloride powder after mixing with binder mixing granulation, using powder co-injection forming technique Shape base is made, product is obtained after degreasing desalination, sintering, which realizes high interfacial bonding strength and reached controllable hole knot Structure realizes near-net-shape in process aspect.
However, antioxygenic property, acid-alkali-corrosive-resisting performance are often very poor, so that filtering body for metal filters Use environment be very limited, service life is shorter；And ceramic filtering body obdurability is low, thermal conductivity is poor, limits pottery The regeneration service life when intensity and use of porcelain filtering body, and often to there is preparation process more multiple for these filtering Antibody Production Techniques It is miscellaneous, the disadvantages of pore structure is single, higher cost.
The performance of inter-metallic compound material has both the obdurability of metal and the resistance to height of ceramics between metal and ceramics Warm nature.China Patent Publication No. CN1640528A has invented the preparation method of Intermatallic Ti-Al compound filter membrane, filters simultaneously Fenestra hole is to be controlled using the inclined diffusion effect of Al element, and the film can be welded with metal, and expand inoranic membrane uses model It encloses.Fe3Si base intermetallic compound is because of its excellent corrosion-resistant, anti-oxidant, rub resistance and prepares that raw material is cheap, preparation method The advantages that easy, it is likely that become a kind of potential structural material, but associated structure function exploitation is not drawn Play the enough attention of people.
Therefore, the present invention proposes design hierarchical porous structure intermetallic compound/ceramic composite filtering body, utilizes material Between in-situ authigenic react to form intermetallic compound and ceramic composite, by different-grain diameter reaction mass layering, be in Gradient base, non-pressure underground irrigation from bottom to top, form multistage gradient hole, had both ensured high intensity, the high thermal conductivity of material in the process Property, erosion resistance, high temperature resistance, further through multistage gradient pore structure design and prepare, while improve porosity and filtering effect Rate.
Summary of the invention
In order to overcome metal filters antioxygenic property and acid-alkali-corrosive-resisting performance is poor and ceramic filtering body is tough simultaneously Property the low and poor technological deficiency of thermal conductivity, the present invention provides a kind of multistage hole composite material filtering body.
Present invention simultaneously provides the preparation methods of this filtering body.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of multistage hole composite material filtering body, which is characterized in that it is the Fe powder, Si powder, Al powder, Ti with different-grain diameter Powder, SiCwPowder, B4C powder is raw material, is pressed into from bottom to top using layering compression-moulding methods, mixed raw material particle scale is successively The round billet body of increase, it is also to be gradually increased that the thickness of every layer of round billet body is lower from bottom to top, then by the round billet of compression moulding Body carries out segmentation pressureless sintering, to be formed from bottom to top, the filtering body in aperture gradually multistage apertures of bigger difference；This mistake The skeleton of filter body is by Fe3(Si1-x,Alx) intermetallic compound base body surrounds SiCw、B4C particle is constituted, a small amount of TiC+Fe3(C, B) distribution of particles is in Fe3(Si1-x,Alx) in, and SiCwWhisker (coarse) and TiB whisker (reaction is formed, tiny) are distributed in hole In, Ti2SiC is then because depending on SiCwIt grows and is included in SiCwOn whisker.
Above-mentioned every layer of round billet body material molar ratio is Fe:Si:Al:Ti:SiCw: B4C=3:1:1:0.3:1:1；In-situ authigenic Reaction equation are as follows: 3Fe+Si+Al+0.3Ti+SiCw+B4C→Fe3(Si1-x, Alx)+SiCw+B4The a small amount of Ti of C+2SiC+TiB+TiC+Fe3 (C,B)。
Multistage hole composite material filtering body of the invention the preparation method comprises the following steps:
Step 1: the preparation of composite porous raw material
First prepare Fe powder, Si powder, Al powder, the Ti powder, SiC of different-grain diameter rangewPowder and B4C powder, that is to say, that six kinds of originals Beginning powder includes different-grain diameter section；
Step 2: composite porous powder mixing prepares
The ready starting powder of the first step is mixed into multiple groups at change of gradient according to partial size and mixes starting powder, it is desirable that In every group of mixing starting powder, the proportion of six kinds of starting powders is equal are as follows: Fe:Si:Al:Ti:SiCw: B4C=3:1:1:0.3:1:1；
Step 3: composite porous compression moulding
Above-mentioned partial size is mixed into starting powder at the multiple groups of change of gradient, in such a way that partial size is gradually increased from top to bottom Layering is fitted into mold, every to fill a lamination one-pass molding, is finally pressed into round billet；It is required that from top to bottom, every layer of mixed-powder The green body thickness being pressed into is sequentially increased:
Step 4: composite porous reaction-sintered
Segmentation pressureless sintering is carried out by calcination temperature is gradually increased after the round billet drying of compression moulding, passes through reaction-sintered mistake Diffusive migration in journey, to form fine and close aperture into the composite porous of gradient distribution.
Further, particle size range is respectively as follows: Si powder after six kinds of raw material grindings, Ti powder is 5~50 μm, Al powder in second step For 10~50, B4C is 1~10 μm, and SiC diameter of whiskers is 1~5 μm, and draw ratio is 5~15.
Further, the round billet being finally pressed into is divided into three layers in third step, in which:
(1) bottom particle is most thin: Fe powder, Si powder, Ti powder are 5~10 μm, and Al powder is 10~20 μm, B4C is 1~3 μm, SiC diameter of whiskers is 1~5 μm, and draw ratio is less than 5,2~3mm of blank thickness；
(2) intermediate layer granulate increases: Fe powder, Si powder, Ti powder are 10~30 μm, and Al powder is 20~30 μm, B4C is 3~6 μ M, SiC diameter of whiskers are 1~5 μm, and draw ratio is less than 10,5~7mm of blank thickness；
(3) top layer's particle is maximum: Fe powder, Si powder, Ti powder are 30~50 μm, and Al powder is 30~50 μm, B4C is 6~10 μ M, SiC diameter of whiskers are 1~5 μm, and draw ratio is less than 15, blank thickness 10mm.
Further, the 4th step is divided into two sections when calcining, the first stage is heated to 650 DEG C with 4 DEG C/mi4 of heating rate, heat preservation 2~3h is chiefly to facilitate Al diffusion, so that Al particle quickly spreads in the state of close to fusing point, reacts, with Fe, Si particle In conjunction with, and the three-dimensional communication hole that reaction is formed is left at original each Al particle position；Second segment is 8 with heating rate DEG C/mi4, temperature is promoted to 1200 DEG C~1300 DEG C, soaking time 3h is chiefly to facilitate Fe3(Si1-x,Alx) formed, and with SiCwWhisker, B4C particle combines, and obtains composite material；Pass through the diffusive migration during reaction-sintered, Fe3(Si1-x,Alx) at SiC is surrounded for matrixwWhisker, B4C particle forms the porous compound of densification.
Further, drying described in the 4th step refers to dries 2h in drying box at 50 DEG C.
Illustrate the positive effect of the present invention below according to reaction of the invention and the mechanism of action.
1, the present invention is reacted using in-situ authigenic of material during non-pressure underground irrigation: 3Fe+Si+Al+0.3Ti+ SiCw+B4C→Fe3(Si1-x, Alx)+SiCw+B4The a small amount of Ti of C+2SiC+TiB+TiC+Fe3(C, B) forms Fe3(Si1-x,Alx) gold Compound and SiC between categoryw、B4The composite material of the ceramics such as C；Second is that various sizes of reaction mass, layering base in gradient, according to By without the particle packing physics pore-creating in pressure reaction process, reaction pore-forming, can be formed in the composite has multilevel size Gradient pore；The superiority of this porous material is: 1. because intermetallic compound is matrix, thermal conductivity is high, and in Fe3 (Si1-x,Alx) in because solid solution Al, and skeleton surface formed Al2O3Protective film, corrosion-resistant, anti-oxidant, rub resistance；While because For there are SiC in skeletonw、B4The ceramic phases such as C, and improve intensity, reduce linear expansion coefficient, to reduce regeneration heating stress.Cause This, from the point of view of material property, the existing good erosion-wear-resisting performance of porous material, and have good regenerability, extension makes Use the service life；2. hole is three-dimensional communication, aperture is the multistage of gradient, is covered with thick, the fine grain palpus being interspersed in hole.
2, it is with Fe powder, Si powder, Al powder, Ti powder, SiC that the present invention is composite porouswPowder, B4C powder is raw material, by anti- Synthesis should be sintered to be made, simple process and low cost.By changing pressure, raw material particle size, the aperture size of filtering body is come Regulate and control porosity.Porosity had not only been improved in this way and has reduced filtration resistance, but also can improve filter efficiency and precision, and make particulate matter not It preferably blocks, is easily reversed flushing regeneration etc..Invention filtering preparation process is simple, and raw material sources are extensive, low in cost, is applicable in In automobile, chemical industry, metallurgy industry tail gas, effluent purifying filter assemblies, the supporter etc. of photo-thermal sea water desalination.3, the present invention is more Porous materials are with Fe3(Si1-x,Alx) as matrix encirclement SiCw、B4C particle forms fine and close skeleton, and is formed on skeleton surface Al2O3Protective film, corrosion-resistant, inoxidizability, rub resistance；Simultaneously as there are SiC in skeletonw、B4The ceramic phases such as C, and improve strong Degree reduces linear expansion coefficient, to reduce regeneration heating stress.
4, the present invention is composite porous from top to bottom, and aperture reduces, and has the characteristics that bore diameter gradient；All it is covered in hole SiCwWith TiB whisker, porosity 45.7~66.2%, compression strength is 45.3~73.5MPa.Particle size is adjusted, can be adjusted Aperture, porosity, minimax aperture and the gradient of whole porous material.This structure is conducive to improve the hole of porous material Rate reduces pressure drop, while improving filtering accuracy and efficiency, and is conducive to backwash regeneration.
The porosity of porous material of the present invention and the detection method of compression strength are respectively according to national standard GB/T1966-1996.,
Detailed description of the invention
The die-filling schematic diagram of Fig. 1 different-grain diameter raw material；
Fig. 2 filtering body pore structure schematic diagram；
Fig. 3-filtering body lowest level pore structure shape appearance figure.
In figure: the upper layer 1-, the middle layer 2-, 3- lower layer
Specific embodiment
Preparation process of the present invention is further illustrated with reference to the accompanying drawings and examples.
Multistage hole composite material filtering body of the invention the preparation method comprises the following steps:
Step 1: the preparation of composite porous raw material
Prepare Fe powder, Si powder, Al powder, the Ti powder, SiC of different-grain diameter range in advancewPowder and B4C powder, specific as follows:
Fe powder, Si powder, Ti powder are 5~10 μm, 10~30 μm and 30~50 μm three sections of particle size ranges；
Al powder is 10~20 μm, 20~30 μm and 30~50 μm three sections of particle size ranges；
B4C is 1~3 μm, 3~6 μm and 6~10 μm three sections of particle size ranges；
SiC is that diameter of whiskers is 1~5 μm, draw ratio less than 5, diameter be 1~5 μm, draw ratio less than 10, diameter be 1~ 5 μm, three kind scales of the draw ratio less than 15；
Step 2: composite porous powder mixing prepares
By the Fe powder of above-mentioned particle size range, Si powder, Al powder, Ti powder, SiCwPowder, B4Six kinds of powder of C powder, according to partial size in ladder Degree variation ball milling is mixed into three groups of mixing starting powders, and in three groups of mixing starting powders, the proportion of six kinds of powder is equal are as follows: Fe:Si: Al:Ti:SiCw: B4C=3:1:1:0.3:1:1；
Divide three layers in such a way that partial size from top to bottom is gradually increased for above-mentioned three groups of mixing starting powders to be fitted into mold, Wherein:
Bottom particle is most thin: Fe powder, Si powder, Ti powder are 5~10 μm, and Al powder is 10~20 μm, B4C is 1~3 μm, SiC Diameter of whiskers is 1~5 μm, and draw ratio is less than 5,2~3mm of blank thickness；
Intermediate layer granulate increases: Fe powder, Si powder, Ti powder are 10~30 μm, and Al powder is 20~30 μm, B4C is 3~6 μm, SiC diameter of whiskers is 1~5 μm, and draw ratio is less than 10,5~7mm of blank thickness；
Top layer's particle is maximum: Fe powder, Si powder, Ti powder are 30~50 μm, and Al powder is 30~50 μm, B4C is 6~10 μm, SiC diameter of whiskers is 1~5 μm, and draw ratio is less than 15, blank thickness 10mm.
It is required that every fill a lamination one-pass molding, it is finally pressed into round billet as shown in Figure 1；Round billet as can be seen from Figure 1 It is divided into upper layer 1, middle layer 2 and lower layer 3, the thickness and partial size of 3 mixed-powder of upper layer 1, middle layer 2 and lower layer successively decrease.
Step 4: composite porous reaction-sintered
Segmentation pressureless sintering is carried out after the green body of compression moulding is put into drying box at 50 DEG C dry 2h.First stage master If promoting Al diffusion.650 DEG C are heated to 4 DEG C/min of heating rate, keeps the temperature 2~3h, so that Al particle is close to fusing point It quickly spreads, react under state, in conjunction with Fe, Si particle, and leave what reaction was formed at original each Al particle position Three-dimensional communication hole.Second segment is chiefly to facilitate Fe3(Si1-x,Alx) formed, and and SiCwWhisker, B4C particle combines, and is answered Condensation material.It is 8 DEG C/min with heating rate, temperature is promoted to 1200 DEG C~1300 DEG C, soaking time 3h.Pass through reaction-sintered Diffusive migration in the process, Fe3(Si1-x,Alx) become matrix encirclement SiCwWhisker, B4C particle forms the porous compound of densification The skeleton of material.Specific reaction equation are as follows:
(1)3Fe+Si+Al→Fe3(Si1-x,Alx)
(2)5Ti+B4C→4TiB+TiC
(3)Fe+B4C→Fe3(C,B)+FeB+Fe2B
(4)2Ti+SiC→Ti2SiC
Above-mentioned reaction merges are as follows:
(5)3Fe+Si+Al+0.3Ti+SiCw+B4C→Fe3(Si1-x,Alx)+SiCw+B4The a small amount of Ti of C+2SiC+TiB+TiC+ Fe3(C,B)
Wherein SiCw、B4C primarily serves additional ceramics effect, while again because of a small amount of decomposition, and provides the source Si, B, C, with Ti, Fe is respectively formed a small amount of Ti2SiC、TiB、TiC、Fe3(C, B), to Fe3(Si1-x,Alx) matrix plays invigoration effect.
In order to verify the positive effect of the present invention, after sintering, porous body of the invention is cooled to the furnace 450 DEG C After take out and cool down in air, then the performance of material is detected with structure and morphology, it is found that after reaction-sintered, instead The three-dimensional communication hole for answering accumulation physical holes between composition granule, reaction to be formed, forms different multistage apertures, and pore diameter range is 5~ Between 60 μm, top layer is 35~60 μm of aperture, and about 10 μm of thickness, middle layer is 10~35 μm, about 5 μm of thickness, and lowest level Aperture is 5~10 μm, about 2 μm of thickness.From top to bottom, aperture is smaller, and thickness is thinner；All it is covered with SiC in holewWith TiB whisker, hole Gap rate 45.7~66.2%, compression strength are 45.3~73.5MPa, filtering body pore structure pattern such as attached drawing 2- filtering body of the present invention Pore structure is as shown in Fig. 2, attached drawing 3 shows filtering body lowest level pore structure pattern, it can be seen from the figure that hole is three-dimensional connects Logical, thick, the fine grain palpus being interspersed are covered in hole.Adjust particle size, the aperture of adjustable porous material, porosity, Minimax aperture and gradient.This hierarchical porous structure is conducive to improve the porosity of porous material, reduces pressure drop, improves simultaneously Filtering accuracy and efficiency, and be conducive to backwash regeneration.

Claims (7)

1.一种多级孔复合材料过滤体，其特征在于，它是以不同粒径的Fe粉、Si粉、Al粉、Ti粉、SiCw粉、B4C粉为原料，采用分层模压成型方法压制成自下而上，混合原料颗粒尺度依次增大的圆坯体，每层圆坯体的的厚度自下而上下也是逐渐增大的，然后将压制成型的圆坯体进行分段无压烧结，从而形成自下而上，孔径逐渐越大的不同多级孔径的过滤体；这种过滤体的骨架由Fe3(Si1-x,Alx)金属间化合物基体包围着SiCw、B4C颗粒构成，少量TiC+Fe3(C,B)颗粒分布在Fe3(Si1-x,Alx)中，而SiCw晶须(粗大)和TiB晶须(反应形成，细小)分布在孔洞中，Ti2SiC则因依附于SiCw生长而包括在SiCw晶须上；1. a multi-level porous composite filter body, is characterized in that, it is raw material with Fe powder, Si powder, Al powder, Ti powder, SiC w powder, B 4 C powder of different particle diameters, adopts layered molding The molding method is pressed into a round blank with the particles of mixed raw materials increasing sequentially from bottom to top. Pressureless sintering to form filter bodies with different multi-stage pore sizes from bottom to top and gradually larger pore sizes; the skeleton of this filter body is surrounded by Fe 3 (Si 1-x , Al x ) intermetallic compound matrix surrounded by SiC w , B 4 C particles, a small amount of TiC+Fe 3 (C, B) particles are distributed in Fe 3 (Si 1-x , Al x ), while SiC w whiskers (coarse) and TiB whiskers (reaction formation, fine ) distributed in the pores, and Ti 2 SiC is included on the SiC w whiskers because it is attached to the SiC w growth; 上述每层圆坯体原料摩尔比为Fe：Si：Al：Ti：SiCw：B4C＝3：1：1：0.3：1：1；原位自生反应式为：3Fe+Si+Al+0.3Ti+SiCw+B4C→Fe3(Si1-x，Alx)+SiCw+B4C+少量Ti2SiC+TiB+TiC+Fe3(C,B)。The molar ratio of raw materials for each layer of circular blanks is Fe:Si:Al:Ti: SiCw :B 4 C=3:1:1:0.3:1:1; the in-situ autogenous reaction formula is: 3Fe+Si+Al+ 0.3Ti+SiC w +B 4 C→Fe 3 (Si 1-x , Al x )+SiC w +B 4 C+a small amount of Ti 2 SiC+TiB+TiC+Fe 3 (C,B). 2.一种制备多级孔复合材料过滤体的方法，其特征在于，2. a method for preparing a multi-stage porous composite filter body, characterized in that, 第一步：多孔复合材料原料的制备Step 1: Preparation of porous composite materials 先准备不同粒径范围的Fe粉、Si粉、Al粉、Ti粉、SiCw粉和B4C粉，也就是说，六种原始粉末均包括不同粒径段；First prepare Fe powder, Si powder, Al powder, Ti powder, SiC w powder and B 4 C powder with different particle size ranges, that is to say, the six original powders all include different particle size segments; 第二步：多孔复合材料粉体混合准备Step 2: Preparation of Porous Composite Powder Mixing 将第一步准备好的原始粉末按照粒径成梯度变化混合成多组混合原始粉末，要求每组混合原始粉末中，六种原始粉末的配比均为：Fe：Si：Al：Ti：SiCw：B4C＝3：1：1：0.3：1：1；The original powder prepared in the first step is mixed into multiple groups of mixed original powders according to the particle size gradient. w : B 4 C=3:1:1:0.3:1:1; 第三步：多孔复合材料的压制成型Step 3: Compression molding of porous composites 将上述粒径成梯度变化的多组混合原始粉末，按照从下到上粒径逐渐增大的方式分层装入模具中，每装一层压制一次成型，最终压制成圆坯；要求从下到上，每层混合粉末压制成的坯体厚度依次增大：The above-mentioned multiple groups of mixed original powders with gradient changes in particle size are loaded into the mold in layers in a manner that the particle size gradually increases from bottom to top, and each layer is pressed once for molding, and finally pressed into a round blank; Up to the above, the thickness of the green body pressed by each layer of mixed powder increases in turn: 第四步：多孔复合材料的反应烧结Step 4: Reaction Sintering of Porous Composites 将压制成型的圆坯干燥后逐渐提高煅烧温度进行分段无压烧结，通过反应烧结过程中的扩散迁移，从而形成致密的孔径成梯度分布的多孔复合材料。After drying the compacted round blank, the calcination temperature is gradually increased to carry out staged pressureless sintering, and through the diffusion and migration in the process of reaction sintering, a dense porous composite material with a gradient distribution of pore size is formed. 3.如权利要求2所述的制备多级孔复合材料过滤体的方法，其特征在于，第二步中，六种原料研磨后粒径范围分别为：Si粉、Ti粉为5～50μm，Al粉为10～50，B4C为1～10μm，SiC晶须直径为1～5μm，长径比为5～15。3. The method for preparing a multi-stage porous composite filter body as claimed in claim 2, wherein in the second step, the particle size ranges after grinding of the six raw materials are respectively: Si powder and Ti powder are 5-50 μm, The Al powder is 10-50, the B 4 C is 1-10 μm, the SiC whisker diameter is 1-5 μm, and the aspect ratio is 5-15. 4.如权利要求2所述的制备多级孔复合材料过滤体的方法，其特征在于，第三步中，最终压制成的圆坯分为三层，其中：4. The method for preparing a multi-stage porous composite filter body as claimed in claim 2, wherein in the third step, the final pressed round blank is divided into three layers, wherein: (1)最底层颗粒最细：Fe粉、Si粉、Ti粉为5～10μm，Al粉为10～20μm，B4C为1～3μm，SiC晶须直径为1～5μm，长径比小于5，原坯厚度2～3mm；(1) The particles at the bottom layer are the finest: Fe powder, Si powder, Ti powder are 5-10 μm, Al powder is 10-20 μm, B 4 C is 1-3 μm, SiC whisker diameter is 1-5 μm, and the aspect ratio is less than 5. The thickness of the original billet is 2～3mm; (2)中间层颗粒增大：Fe粉、Si粉、Ti粉为10～30μm，Al粉为20～30μm，B4C为3～6μm，SiC晶须直径为1～5μm，长径比小于10，原坯厚度5～7mm；(2) The particles of the intermediate layer increase: Fe powder, Si powder, Ti powder are 10-30 μm, Al powder is 20-30 μm, B 4 C is 3-6 μm, SiC whisker diameter is 1-5 μm, and the aspect ratio is less than 10. The thickness of the original billet is 5～7mm; (3)最上层颗粒最大：Fe粉、Si粉、Ti粉为30～50μm，Al粉为30～50μm，B4C为6～10μm，SiC晶须直径为1～5μm，长径比小于15，原坯厚度10mm。(3) The particles in the uppermost layer are the largest: Fe powder, Si powder, Ti powder are 30-50 μm, Al powder is 30-50 μm, B 4 C is 6-10 μm, SiC whisker diameter is 1-5 μm, and the aspect ratio is less than 15 , the thickness of the original billet is 10mm. 5.如权利要求2所述的制备多级孔复合材料过滤体的方法，其特征在于，第四步的分段无压烧结分为两段，第一阶段以升温速率4℃/min加热到650℃，保温2～3h，主要是促进Al扩散，使得Al颗粒在接近熔点的状态下快速扩散、反应，与Fe、Si颗粒结合，而在原来的每个Al颗粒位置处留下反应形成的三维连通孔洞；第二段以升温速率是8℃/min，将温度提升至1200℃～1300℃，保温时间3h，主要是促进Fe3(Si1-x,Alx)形成，并与SiCw晶须、B4C颗粒结合，获得复合材料；通过反应烧结过程中的扩散迁移，Fe3(Si1-x,Alx)成为基体包围SiCw晶须、B4C颗粒，形成致密的多孔复合。5. The method for preparing a multi-stage porous composite filter body as claimed in claim 2, wherein the staged pressureless sintering in the fourth step is divided into two stages, and the first stage is heated to a temperature of 4°C/min at a heating rate of 650 ℃, heat preservation for 2 to 3 hours, mainly to promote the diffusion of Al, so that the Al particles diffuse and react rapidly in a state close to the melting point, and combine with Fe and Si particles, while leaving the reaction at the original position of each Al particle. Three-dimensional connected pores; the second stage increases the temperature to 1200°C ~ 1300°C at a heating rate of 8°C/min, and the holding time is 3h, mainly to promote the formation of Fe 3 (Si 1-x , Al x ), and with SiC w The whiskers and B 4 C particles are combined to obtain a composite material; through the diffusion and migration during the reaction sintering process, Fe 3 (Si 1-x , Al x ) becomes a matrix to surround the SiC w whiskers and B 4 C particles, forming a dense porous complex. 6.如权利要求2所述的制备多级孔复合材料过滤体的方法，其特征在于，第四步中所述的圆坯干燥是指在干燥箱中50℃下干燥2h。6 . The method for preparing a multi-stage porous composite filter body according to claim 2 , wherein the drying of the round blanks in the fourth step refers to drying in a drying oven at 50° C. for 2 hours. 7 . 7.一种如权利要求1所述的多级孔复合材料过滤体在于汽车、化工、冶金行业尾气、废液净化过滤组件，以及光热海水淡化用的支撑体上的应用。7. The application of the multi-stage porous composite material filter body according to claim 1 in the purification and filter assembly of exhaust gas and waste liquid in automobile, chemical industry and metallurgical industry, and the support body for photothermal seawater desalination.
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