CN101574740A

CN101574740A - Manufacturing method for metal and ceramic gradient composite pipe

Info

Publication number: CN101574740A
Application number: CNA2009103029941A
Authority: CN
Inventors: 赵康; 李大玉; 张宏利; 滕乐天
Original assignee: Xian University of Technology
Current assignee: Xian University of Technology
Priority date: 2009-06-05
Filing date: 2009-06-05
Publication date: 2009-11-11
Anticipated expiration: 2029-06-05
Also published as: CN101574740B

Abstract

The invention discloses a manufacturing method for a metal and ceramic gradient composite pipe, comprising the following steps: manufacturing a metal and inner ceramic gradient composite pipe by utilizing casting rolling technique, at first, obtaining casting slurry in accordance with volume percent of metal and ceramic at each layer of materials forming gradient ingredients, manufacturing the slurry into green compact layers by a casting process, then, as required by material ingredients of the composite pipe from an inner wall to an outer wall, wrapping the green compact layers in sequence on a roller shaft of a double-roller press for rolling formation so as to form a composite pipe biscuit, and sintering the composite pipe biscuit to obtain the metal and ceramic gradient composite pipe. The composite pipe manufactured according to the invention can control pipe diameter, wall thickness and gradient transition manner of pipe wall materials, and has simple manufacturing process and low production cost; the number of transition layers of the manufactured metal and ceramic gradient composite pipe is unlimited, has excellent abrasive resistance, chemical stability, a thermal impact resistance and great economic and social benefits.

Description

The preparation method of metal and ceramic gradient composite pipe

Technical field

The invention belongs to technical field of material, relate to a kind of preparation method of composite, be specifically related to a kind of preparation method of metal and ceramic gradient composite pipe.

Background technology

United States Patent (USP) " a kind of method of utilizing the ceramic-lined hollow body of metal fever prepared in reaction " (application number US-4363832, open day 1982.12.14, publication number: 4363832) disclose a kind of self propagating high temperature synthetic method (SHS) for preparing ceramic liner metal tube, the ceramic liner metal tube that adopts this method to make is applied to the conveying of molten aluminum liquid.Though this method can be carried out cramic coat (comprising the coating that has transition zone) at the inner surface of metal tube, but also there are many technical problems to be solved that have at aspects such as the design of density, uniformity and the combustion process of coating and controls, particularly are being restricted aspect the transition zone number of plies and the thickness.

At present, prior art also has the extrusion modling of the multi-blank of employing, and the method for sintering curing prepares metal and ceramic gradient composite pipe then, to satisfy the specific (special) requirements of equipment such as high-temp combustion device, has prepared two layers, three layers and four layers of gradient composite pipe with this method.But the extruding number of plies of the gradient composite pipe that employing multi-blank extrusion makes generally all is limited in 4 layers, and extrusion process is difficult to control.

Summary of the invention

The preparation method who the purpose of this invention is to provide a kind of metal and ceramic gradient composite pipe, can control the gradient transition mode of multiple tube diameter, pipe thickness and pipe wall material, be not subjected to the restriction of the transition zone number of plies and thickness in the multiple tube, make the fine and close multiple tube uniformly of coating.

The technical solution adopted in the present invention is, the preparation method of metal and ceramic gradient composite pipe, doctor-blade casting process and pair roller roll-in technology are combined, making inwall is that pure ceramic layer, gradient transition are the metal/ceramic multiple tube biscuit of simple metal layer to outer wall, with this multiple tube biscuit sintering curing, making inwall is that pure ceramic outer wall is the metal and ceramic gradient composite pipe of simple metal, and this method is carried out according to the following steps:

Step 1: according to aperture D and the wall thickness H of required preparation metal and ceramic gradient composite pipe; Adopt the gradient transition ratio of each transition zone of the composition multiple tube tube wall corresponding with this multiple tube aperture and multiple tube wall thickness; According to this gradient transition ratio; Get respectively ceramic powders from 100vol.% to 0vol.%; Simultaneously; In the gradient transition ratio identical with this ceramic powders gradient transition ratio; Correspondingly get respectively metal dust from 0vol.% to 100vol.%; The total amount of each ceramic powders of getting and metal dust is 100%

The aperture D of metal/ceramic multiple tube is 10mm≤D≤50mm,

When 1. the thickness of pipe wall H of metal/ceramic multiple tube was 2mm≤H≤20mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤10vol.%,

When 2. the thickness of pipe wall H of metal/ceramic multiple tube was 20mm＜H≤50mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤30vol.%;

The aperture D of metal/ceramic multiple tube is 50mm＜D＜100mm,

When 1. the thickness of pipe wall H of metal/ceramic multiple tube is 10mm≤H≤70mm, the transition ratio 5vol.%≤Φ≤25vol.% of gradient transitional lay,

2. the thickness of pipe wall H of metal/ceramic multiple tube is 70mm＜H≤100mm, the transition ratio 5vol.%≤Φ≤40vol.% of gradient transitional lay;

The aperture D of metal/ceramic multiple tube is 100mm≤D≤200mm,

When 1. the thickness of pipe wall H of metal/ceramic multiple tube is 20mm≤H≤100mm, the transition ratio 5vol.%≤Φ≤30vol.% of gradient transitional lay;

When 2. the thickness of pipe wall H of metal/ceramic multiple tube is 100mm＜H≤200mm, the transition ratio 5vol.%≤Φ≤40vol.% of gradient transitional lay;

Step 2: with the each total amount of getting of step 1 is that 100% ceramic powders and metal dust carry out the planetary ball mill mixing, obtains the different metal/ceramic mixed powder of component volume percent content respectively;

Step 3: the metal/ceramic mixed powder of getting the variant component volume percent content that step 2 makes respectively, even with adhesive and solvent respectively, make the slurry of each transition composition respectively, in this slurry, percentage by volume, metal/ceramic mixed powder are 30%～70%, adhesive is 10%～50%, solvent is 20%～60%, each component total amount 100%, with this slurry sieve respectively, vacuum degassing, obtain the different casting slurry of component volume percent content respectively;

Step 4: according to the aperture D and the wall thickness H of required preparation metal/ceramic multiple tube in the step 1, adopt thickness S with this multiple tube aperture D, wall thickness H and each gradient transitional lay of the corresponding composition multiple tube of gradient transition ratio tube wall, utilize the flow casting molding method, the different casting slurry of the component volume percent content that step 3 is made respectively curtain coating to become thickness be the green layer of S, after this green layer drying, obtain the different green compact of component volume percent content respectively;

When the aperture of metal/ceramic multiple tube D is that 10mm≤D≤50mm, thickness of pipe wall H are 2mm≤H≤20mm and gradient transitional lay transition ratio Φ when being 5vol.%≤Φ≤10vol.%, the thickness S of each gradient transitional lay is 0.1mm≤S≤0.5H,

When the aperture of metal/ceramic multiple tube D is that 10mm≤D≤50mm, thickness of pipe wall H are the transition ratio Φ of 20mm＜H≤50mm and gradient transitional lay when being 5vol.%≤Φ≤30vol.%, the thickness S of each gradient transitional lay is 0.5mm≤S≤0.33H,

When the aperture of metal/ceramic multiple tube D is that 50mm＜D＜100mm, thickness of pipe wall H are the transition ratio Φ of 10mm≤H≤70mm and gradient transitional lay when being 5vol.%≤Φ≤25vol.%, the thickness S of each gradient transitional lay is 0.3mm≤S≤0.4H,

When the aperture of metal/ceramic multiple tube D is that 50mm＜D＜100mm, thickness of pipe wall H are the transition ratio Φ of 70mm＜H≤100mm and gradient transitional lay when being 5vol.%≤Φ≤40vol.%, the thickness S of each gradient transitional lay is 1mm≤S≤0.33H,

When the aperture of metal/ceramic multiple tube D is that 100mm≤D≤200mm, thickness of pipe wall H are the transition ratio Φ of 20mm≤H≤100mm and gradient transitional lay when being 5vol.%≤Φ≤3vol.%, the thickness S of each gradient transitional lay is 0.5mm≤S≤0.25H,

When the aperture of metal/ceramic multiple tube D is that 100mm≤D≤200mm, thickness of pipe wall H are the transition ratio Φ of 100mm＜H≤200mm and gradient transitional lay when being 5vol.%≤Φ≤40vol.%, the thickness S of each gradient transitional lay is 2mm≤S≤0.33H;

Step 5: with thickness is that the organic layer of 0.5mm～2mm is wrapped on the roll shaft of pair roller roll squeezer, the order of successively decreasing according to ceramic powders content, the different green compact of component volume percent content that step 4 is made, the lamination parcel successively from the outside of this organic layer, then, carry out the pair roller roll-forming, making inwall is that pure ceramic outer wall is the metal and ceramic gradient composite pipe biscuit of simple metal;

Step 6: the metal and ceramic gradient composite pipe biscuit that step 5 is made places vacuum or inert gas environment, be under 900～1400 ℃ the condition in temperature, be incubated 2～4 hours, making inwall is that pure ceramic outer wall is the metal and ceramic gradient composite pipe of simple metal.

Another technical scheme of the present invention is, the preparation method of metal and ceramic gradient composite pipe, doctor-blade casting process and pair roller roll-in technology are combined, making inwall is that simple metal layer, gradient transition are the metal/ceramic multiple tube biscuit of pure ceramic layer to outer wall, then, with this multiple tube biscuit sintering curing, make inwall for the simple metal outer wall is the metal and ceramic gradient composite pipe of pure pottery, specifically carry out according to the following steps:

The aperture D of metal/ceramic multiple tube is 10mm≤D≤80mm,

When 2. the thickness of pipe wall H of metal/ceramic multiple tube was 20mm＜H≤50mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤20vol.%,

When 3. the thickness of pipe wall H of metal/ceramic multiple tube was 50mm＜H≤100mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤30vol.%

When the aperture of metal/ceramic multiple tube D is that 10mm≤D≤80mm, thickness of pipe wall H are 2mm≤H≤20mm and gradient transitional lay transition ratio Φ when being 5vol.%≤Φ≤10vol.%, the thickness S of each gradient transitional lay is 0.1mm≤S≤0.5H,

When the aperture of metal/ceramic multiple tube D is that 10mm≤D≤80mm, thickness of pipe wall H are the transition ratio Φ of 20mm＜H≤50mm and gradient transitional lay when being 5vol.%≤Φ≤20vol.%, the thickness S of each gradient transitional lay is 0.5mm≤S≤0.33H,

When the aperture of metal/ceramic multiple tube D is that 10mm≤D≤80mm, thickness of pipe wall H are the transition ratio Φ of 50mm＜H≤100mm and gradient transitional lay when being 5vol.%≤Φ≤30vol.%, the thickness S of each gradient transitional lay is 0.5mm≤S≤0.25H,

Step 5: with thickness is that the organic layer of 0.5mm～2mm is wrapped on the roll shaft of pair roller roll squeezer,

The order of successively decreasing according to metal dust content, the different green compact of component volume percent content that step 4 is made, the outside of this organic layer lamination parcel successively certainly, then, carry out the pair roller roll-forming, making inwall is that pure ceramic outer wall is the metal and ceramic gradient composite pipe biscuit of simple metal;

Step 6: the metal and ceramic gradient composite pipe biscuit that step 5 is made places vacuum or inert gas environment, be under 900 ℃～1400 ℃ the condition in temperature, be incubated 2 hours～4 hours, making inwall is the metal and ceramic gradient composite pipe of pure pottery for the simple metal outer wall.

The inventive method combines casting molding processes and pair roller roll-in technology, preparation carries out the transition to the outer wall simple metal by the pure ceramic gradient of inwall or by the multiple tube of inwall simple metal gradient transition to the pure pottery of outer wall, in the preparation process of multiple tube, can control the gradient transition mode of diameter, pipe thickness and the pipe wall material of multiple tube, preparation process is simple, technology is controlled easily, the transition zone number of plies and the thickness of the metal and ceramic gradient composite pipe that makes are unrestricted, have good wearability, chemical stability and thermal shock resistance.

Description of drawings

Fig. 1 is that the inventive method adopts pair roller roll-forming technology to prepare the schematic diagram of metal and ceramic gradient composite pipe biscuit;

Fig. 2 is the cross section microscopic appearance figure that adopts the metal and ceramic gradient composite pipe that the inventive method makes.

Among the figure, 1. rotating shaft, 2. spring, the 3. back shaft of pipe, 4. green compact, 5. motor, 6. roll shaft.

The specific embodiment

The present invention is described in detail below in conjunction with the drawings and specific embodiments.

In the metal/ceramic composite wood system, ceramic material adopts Al usually ₂O ₃, ZrO ₂, SiO ₂, SiC, TiO ₂And B ₂N ₃Deng.Metal powder material adopts Ni, Cu, Fe, stainless steel, Ag and NiCr alloy etc. usually.

The inventive method adopts doctor-blade casting process to prepare the different metal/ceramic compound green compact layer of constituent content ratio, utilize the pair roller extrusion technique that the green layer that makes is made the multiple tube biscuit then, and, make aperture 10mm～200mm with this multiple tube biscuit sintering curing, wall thickness 2mm～200mm, inwall is pure pottery, gradient ratio transition with 5vol.%～40vol.%, outer wall is the gradient composite pipe or the aperture 10mm～80mm of simple metal, wall thickness 2mm～100mm, inwall is a simple metal, gradient ratio transition with 5vol.%～30vol.%, outer wall is the gradient composite pipe of pure pottery.

With the thickness S of the pure ceramic outer wall simple metal of inwall multiple tube aperture D, thickness of pipe wall S and corresponding each gradient transitional lay of tube wall gradient transition ratio, as shown in table 1; With the thickness S of the pure ceramic inner walls simple metal of outer wall multiple tube aperture D, thickness of pipe wall S and corresponding each gradient transitional lay of tube wall gradient transition ratio, as shown in table 2;

The thickness S of the pure ceramic outer wall simple metal of table 1 inwall multiple tube aperture D, thickness of pipe wall S and corresponding each gradient transitional lay of tube wall gradient transition ratio

The thickness S of the pure ceramic inner walls simple metal of table 2 outer wall multiple tube aperture D, thickness of pipe wall S and corresponding each gradient transitional lay of tube wall gradient transition ratio

Adhesive adopts polyvinyl butyral solution, poly-vinyl alcohol solution or methocel solution in the inventive method; Solvent adopts the isomer of ethanol, propyl alcohol, butanols, amylalcohol, deionized water or toluene or above-mentioned each solvent.

This method employing pair roller roll squeezer prepares the schematic diagram of metal and ceramic gradient composite pipe biscuit, as shown in Figure 1.The pair roller roll squeezer comprises two rotating shafts 1 that be arranged in parallel, two rotating shafts 1 are connected by two springs 2, coaxial respectively back shaft 3 and the roll shaft 6 that is connected with isometric pipe in two rotating shafts 1, the back shaft 3 of pipe and roll shaft 6 are between two springs 2, and concordant setting, two rotating shafts 1 are driven by a motor 5 respectively, and two motor 5 drive two rotating shafts 1 and rotate relatively.The aperture of metal and ceramic gradient composite pipe and length by replacing the pair roller roll squeezer roll shaft 6 and the back shaft 3 of pipe control two springs 2 controls of roll-in pressure by connecting, the roll-in speed of regulating the pair roller roll squeezer by the speed of control motor 5.

During preparation metal and ceramic gradient composite pipe biscuit, with thickness is that the organic layer of 0.5mm～2mm is wrapped on the back shaft 3 of pair roller roll squeezer pipe, then, order of successively decreasing according to the ceramic powders volume percent content or the order of successively decreasing according to the metal dust volume percent content, the green compact 4 that step 4 is made, the lamination parcel successively from the outside of this organic layer, start two motors 5, two motor 5 drive two rotating shafts 1 respectively and rotate relatively, the green compact 4 that are wrapped in the organic layer outside are carried out the pair roller roll-in, and in the roll-in process, two springs 2 make two rotating shafts 1 close gradually, until with green compact 4 roll-formings, make the metal and ceramic gradient composite pipe biscuit.

Embodiment 1

Selecting particle diameter for use is the Al of 0.1～50 μ m ₂O ₃Powder and particle diameter be the Ni powder of 0.1～50 μ m as raw material, preparation aperture 10mm, wall thickness 20mm, inwall are pure Al ₂O ₃Layer, gradient transition ratio are that 5vol.% and outer wall are the multiple tube of pure Ni layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%Ni powder and 100vol.%Al ₂O ₃Powder, 5vol.%Ni powder and 95vol.%Al ₂O ₃Powder, 10vol.%Ni powder and 90vol.%Al ₂O ₃Powder, 15vol.%Ni powder and 85vol.%Al ₂O ₃Powder, 20vol.%Ni powder and 80vol.%Al ₂O ₃Powder, 25vol.%Ni powder and 75vol.%Al ₂O ₃Powder, 30vol.%Ni powder and 70vol.%Al ₂O ₃Powder, 35vol.%Ni powder and 65vol.%Al ₂O ₃Powder, 40vol.%Ni powder and 60vol.%Al ₂O ₃Powder, 45vol.%Ni powder and 55vol.%Al ₂O ₃Powder, 50vol.%Ni powder and 50vol.%Al ₂O ₃Powder, 55vol.%Ni powder and 45vol.%Al ₂O ₃Powder, 60vol.%Ni powder and 40vol.%Al ₂O ₃Powder, 65vol.%Ni powder and 35vol.%Al ₂O ₃Powder, 70vol.%Ni powder and 30vol.%Al ₂O ₃Powder, 75vol.%Ni powder and 25vol.%Al ₂O ₃Powder, 80vol.%Ni powder and 20vol.%Al ₂O ₃Powder, 85vol.%Ni powder and 15vol.%Al ₂O ₃Powder, 90vol.%Ni powder and 10vol.%Al ₂O ₃Powder, 95vol.%Ni powder and 5vol.%Al ₂O ₃Powder, 100vol.%Ni powder and 0vol.%Al ₂O ₃Powder; The mixture of obtaining of respectively organizing is carried out planetary ball mill respectively and mixes, obtain the component percent by volume different respectively organize Ni/Al ₂O ₃Mixed powder; With each group Ni/Al ₂O ₃Mixed powder mixes with polyvinyl butyral solution and ethanol respectively, makes slurry respectively, in this slurry, and percentage by volume, Ni/Al ₂O ₃Mixed powder is 30%, polyvinyl butyral solution is 50%, ethanol is 20%, with the vacuum degassing of sieving of this slurry, obtains casting slurry; Utilize the flow casting molding method, this casting slurry curtain coating is become thickness and multiple tube diameter, pipe thickness and the corresponding green layer of gradient transition ratio; The thickness of each green layer is respectively 0vol.%Ni/100vol.%Al ₂O ₃Layer thickness is 1000 μ m, 5vol.%Ni/95vol.%Al ₂O ₃Layer thickness is 950 μ m, 10vol.%Ni/90vol.%Al ₂O ₃Layer thickness is 950 μ m, 15vol.%Ni/85vol.%Al ₂O ₃Layer thickness is 950 μ m20vol.%Ni/80vol.%Al ₂O ₃Layer thickness is 950 μ m, 25vol.%Ni/75vol.%Al ₂O ₃Layer thickness is 950 μ m, 30vol.%Ni/70vol.%Al ₂O ₃Layer thickness is 950 μ m, 35vol.%Ni/65vol.%Al ₂O ₃Layer thickness is 950 μ m, 40vol.%Ni/60vol.%Al ₂O ₃Layer thickness is 950 μ m, 45vol.%Ni/55vol.%Al ₂O ₃Layer thickness is 950 μ m, 50vol.%Ni/50vol.%Al ₂O ₃Layer thickness is 950 μ m, 55vol.%Ni/45vol.%Al ₂O ₃Layer thickness is 950 μ m, 60vol.%Ni/40vol.%Al ₂O ₃Layer thickness is 950 μ m, 65vol.%Ni/35vol.%Al ₂O ₃Layer thickness is 950 μ m, 70vol.%Ni/30vol.%Al ₂O ₃Layer thickness is 950 μ m, 75vol.%Ni/25vol.%Al ₂O ₃Layer thickness is 950 μ m, 80vol.%Ni/20vol.%Al ₂O ₃Layer thickness is 950 μ m, 85vol.%Ni/15vol.%Al ₂O ₃Layer thickness is 950 μ m, 90vol.%Ni/10vol.%Al ₂O ₃Layer thickness is 950 μ m, 95vol.%Ni/5vol.%Al ₂O ₃Layer thickness is 950 μ m, 100vol.%Ni/0vol.%Al ₂O ₃Layer thickness is 950 μ m, with above-mentioned green layer drying, obtains the different green compact of component volume percent content.With thickness is that the organic layer of 0.5mm is wrapped on the roll shaft of pair roller roll squeezer, presses Al then ₂O ₃The order that percent by volume is successively decreased, with the green compact that make from the outside of this organic layer lamination parcel successively, and, make the interior Al of outer Ni/ by pair roller roll squeezer roll-forming ₂O ₃The gradient composite pipe biscuit, in the roll-forming process, the control roll pressure pressure is 30MPa, roll-in speed is 0.5cm/min; Afterwards, should the interior Al of outer Ni/ ₂O ₃It is 1400 ℃ vacuum environment insulation 2 hours that the gradient composite pipe biscuit places temperature, makes the interior Al of outer Ni/ ₂O ₃Gradient composite pipe.

Embodiment 2

Selecting particle diameter for use is the TiO of 0.1～50 μ m ₂Powder and particle diameter be the Cu powder of 0.1～50 μ m as raw material, preparation aperture 50mm, wall thickness 11mm, inwall are pure TiO ₂Layer, gradient transition ratio are that 10vol.%, outer wall are the multiple tube of pure Cu layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%Cu powder and 100vol.%TiO ₂Powder, 10vol.%Cu powder and 90vol.%TiO ₂Powder, 20vol.%Cu powder and 80vol.%TiO ₂Powder, 30vol.%Cu powder and 70vol.%TiO ₂Powder, 40vol.%Cu powder and 60vol.%TiO ₂Powder, 50vol.%Cu powder and 50vol.%TiO ₂Powder, 60vol.%Cu powder and 40vol.%TiO ₂Powder, 70vol.%Cu powder and 30vol.%TiO ₂Powder, 80vol.%Cu powder and 20vol.%TiO ₂Powder, 90vol.%Cu powder and 10vol.%TiO ₂Powder, 100vol.%Cu powder and 0vol.%TiO ₂Powder; The mixture of obtaining of respectively organizing is carried out planetary ball mill respectively and mixes, obtain the component percent by volume different respectively organize Cu/TiO ₂Mixed powder; With each group Cu/TiO ₂Mixed powder mixes with poly-vinyl alcohol solution and deionized water respectively, makes slurry respectively, in this slurry, and percentage by volume, Cu/TiO ₂Mixed powder is 70%, poly-vinyl alcohol solution is 10%, deionized water is 20%, with the vacuum degassing of sieving of this slurry, obtains casting slurry; Utilize the flow casting molding method, this casting slurry curtain coating is become thickness and multiple tube diameter, pipe thickness and the corresponding green layer of gradient transition ratio; The thickness of each green layer is respectively: 0vol.%Cu/100vol.%TiO ₂Layer thickness is 1000 μ m, 10vol.%Cu/90vol.%TiO ₂Layer thickness is 1000 μ m, 20vol.%Cu/80vol.%TiO ₂Layer thickness is 1000 μ m μ, 30vol.%Cu/70vol.%TiO ₂Layer thickness is 1000 μ m, 40vol.%Cu/60vol.%TiO ₂Layer thickness is 1000 μ m, 50vol.%Cu/50vol.%TiO ₂Layer thickness is 1000 μ m, 60vol.%Cu/40vol.%TiO ₂Layer thickness is 1000 μ m, 70vol.%Cu/30vol.%TiO ₂Layer thickness is 1000 μ m, 80vol.%Cu/20vol.%TiO ₂Layer thickness is 1000 μ m, 90vol.%Cu/10vol.%TiO ₂Layer thickness is 1000 μ m, 100vol.%Cu/0vol.%TiO ₂Layer thickness is 1000 μ m, with above-mentioned green layer drying, obtains the different green compact of component volume percent content.With thickness is that the organic layer of 2mm is wrapped on the roll shaft of pair roller roll squeezer, presses TiO then ₂The order that percent by volume is successively decreased, with the green compact that make from the outside of this organic layer lamination parcel successively, by pair roller roll squeezer roll-forming, make the interior TiO of outer Cu/ ₂The gradient composite pipe biscuit, in the roll-forming process, the control roll pressure pressure is 10MPa, roll-in speed is 1.5cm/min, afterwards, should the interior TiO of outer Cu/ ₂Is it 900 that the gradient composite pipe biscuit places temperature? argon gas atmosphere in insulation 3 hours, make the interior TiO of outer Cu/ ₂Gradient composite pipe.

Embodiment 3

Selecting particle diameter for use is the ZrO of 0.1～50 μ m ₂Powder and particle diameter be the SUS316L stainless steel powder of 0.1～50 μ m as raw material, preparation aperture 30mm, wall thickness 2mm, inwall are pure ZrO ₂Layer, gradient transition ratio are that 8vol.%, outer wall are the multiple tube of pure SUS316L stainless steel layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%SUS316L stainless steel powder and 100vol.%ZrO ₂Powder, 8vol.%SUS316L stainless steel powder and 92vol.%ZrO ₂Powder, 16vol.%SUS316L stainless steel powder and 84vol.%ZrO ₂Powder, 24vol.%SUS316L stainless steel powder and 76vol.%ZrO ₂Powder, 32vol.%SUS316L stainless steel powder and 68vol.%ZrO ₂Powder, 40vol.%SUS316L stainless steel powder and 60vol.%ZrO ₂Powder, 48vol.%SUS316L stainless steel powder and 52vol.%ZrO ₂Powder, 56vol.%SUS316L stainless steel powder and 44vol.%ZrO ₂Powder, 64vol.%SUS316L stainless steel powder and 36vol.%ZrO ₂Powder, 72vol.%SUS316L stainless steel powder and 28vol.%ZrO ₂Powder, 80vol.%SUS316L stainless steel powder and 20vol.%ZrO ₂Powder, 88vol.%SUS316L stainless steel powder and 12vol.%ZrO ₂Powder, 96vol.%SUS316L stainless steel powder and 4vol.%ZrO ₂Powder, 100vol.%SUS316L stainless steel powder and 0vol.%ZrO ₂Powder; The mixture of obtaining of respectively organizing is carried out the planetary ball mill mixing respectively, obtain the different SUS316L stainless steel/ZrO of component percent by volume ₂Mixed powder; With each group SUS316L stainless steel/ZrO ₂Mixed powder mixes with methocel solution and propyl alcohol respectively, makes slurry respectively, in this slurry, percentage by volume, the metal/ceramic mixed powder is 30%, methocel solution is 10%, propyl alcohol is 60%, with the vacuum degassing of sieving of this slurry, obtains casting slurry; Utilize the flow casting molding method, this casting slurry curtain coating is become thickness and multiple tube diameter, pipe thickness and the corresponding green layer of gradient transition ratio, the thickness of each green layer is respectively 0vol.%SUS316L stainless steel/100vol.%ZrO ₂Layer thickness is 180 μ m, 8vol.%SUS316L stainless steel/92vol.%ZrO ₂Layer thickness is 140 μ m, 16vol.%SUS316L stainless steel/84vol.%ZrO ₂Layer thickness is 140 μ m, 24vol.%SUS316L stainless steel/76vol.%ZrO ₂Layer thickness is 140 μ m, 32vol.%SUS316L stainless steel/68vol.%ZrO ₂Layer thickness is 140 μ m, 40vol.%SUS316L stainless steel/60vol.%ZrO ₂Layer thickness is 140 μ m, 48vol.%SUS316L stainless steel/52vol.%ZrO ₂Layer thickness is 140 μ m, 56vol.%SUS316L stainless steel/44vol.%ZrO ₂Layer thickness is 140 μ m, 64vol.%SUS316L stainless steel/32vol.%ZrO ₂Layer thickness is 140 μ m, 72vol.%SUS316L stainless steel/28vol.%ZrO ₂Layer thickness is 140 μ m, 80vol.%SUS316L stainless steel/20vol.%ZrO ₂Layer thickness is 140 μ m, 88vol.%SUS316L stainless steel/12vol.%ZrO ₂Layer thickness is 140 μ m, 96vol.%SUS316L stainless steel/4vol.%ZrO ₂Layer thickness is 140 μ m, 100vol.%SUS316L stainless steel/0vol.%ZrO ₂Layer thickness is 140 μ m powder; With above-mentioned green layer drying, obtain the different green compact of component volume percent content.With thickness is that the organic layer of 1.5mm is wrapped on the roll shaft of pair roller roll squeezer, presses ZrO then ₂The order that percent by volume is successively decreased, with the green compact that make from the outside of this organic layer lamination parcel successively, and, make SUS316L stainless steel/ZrO by pair roller roll squeezer roll-forming ₂The gradient composite pipe biscuit, in the roll-forming process, the control roll pressure pressure is 5MPa, roll-in speed is 1cm/min, afterwards, with this SUS316L stainless steel/ZrO ₂Is it 1300 that the gradient composite pipe biscuit places temperature? vacuum environment in the insulation 3 hours, make outer SUS316L stainless steel/interior ZrO ₂Gradient composite pipe.Should outer SUS316L stainless steel/interior ZrO ₂The cross section microscopic appearance figure of gradient composite pipe, as shown in Figure 2, as can be seen from Figure, this gradient composite pipe cross section composition transition good, the gradient layer interface is in conjunction with closely.

Embodiment 4

Select for use particle diameter be the kaolin powder of 0.1～50 μ m and Fe powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 10mm, wall thickness 21mm, inwall are that washed kaolin layer, gradient transition ratio are that 5vol.%, outer wall are the multiple tube of pure Fe layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%Fe powder of mixture and 100vol.% kaolin powder, 5vol.%Fe powder and 95vol.% kaolin powder, 10vol.%Fe powder and 90vol.% kaolin powder, 15vol.%Fe powder and 85vol.% kaolin powder, 20vol.%Fe powder and 80vol.% kaolin powder, 25vol.%Fe powder and 75vol.% kaolin powder, 30vol.%Fe powder and 70vol.% kaolin powder, 35vol.%Fe powder and 65vol.% kaolin powder, 40vol.%Fe powder and 60vol.% kaolin powder, 45vol.%Fe powder and 55vol.% kaolin powder, 50vol.%Fe powder and 50vol.% kaolin powder, 55vol.%Fe powder and 45vol.% kaolin powder, 60vol.%Fe powder and 40vol.% kaolin powder, 65vol.%Fe powder and 35vol.% kaolin powder, 70vol.%Fe powder and 30vol.% kaolin powder, 75vol.%Fe powder and 25vol.% kaolin powder, 80vol.%Fe powder and 20vol.% kaolin powder, 85vol.%Fe powder and 15vol.% kaolin powder, 90vol.%Fe powder and 10vol.% kaolin powder, 95vol.%Fe powder and 5vol.% kaolin powder, 100vol.%Fe powder and 0vol.% kaolin powder; The mixture of obtaining of respectively organizing is carried out planetary ball mill respectively and mixes, obtain the component percent by volume different respectively organize Fe/ kaolin mixed powder; Each group Fe/ kaolin mixed powder is mixed with polyvinyl butyral solution and ethanol respectively, make slurry respectively, in this slurry, percentage by volume, the metal/ceramic mixed powder is 50%, polyvinyl butyral solution is 30%, ethanol is 20%, with the vacuum degassing of sieving of this slurry, obtain casting slurry; Utilize the flow casting molding method, this casting slurry curtain coating is become thickness and multiple tube diameter, pipe thickness and the corresponding green layer of gradient transition ratio; It is 1000 μ m that the thickness of each green layer is respectively 0vol.%Fe/100vol.% kaolin layer thickness, 5vol.%Fe/95vol.% kaolin layer thickness is 1000 μ m, 10vol.%Fe/90vol.% kaolin layer thickness is 1000 μ m, 15vol.%Fe/85vol.% kaolin layer thickness is that 1000 μ m20vol.%Fe/80vol.% kaolin layer thicknesses are 1000 μ m, 25vol.%Fe/75vol.% kaolin layer thickness is 1000 μ m, 30vol.%Fe/70vol.% kaolin layer thickness is 1000 μ m, 35vol.%Fe/65vol.% kaolin layer thickness is 1000 μ m, 40vol.%Fe/60vol.% kaolin layer thickness is 1000 μ m, 45vol.%Fe/55vol.% kaolin layer thickness is 1000 μ m, 50vol.%Fe/50vol.% kaolin layer thickness is 1000 μ m, 55vol.%Fe/45vol.% kaolin layer thickness is 1000 μ m, 60vol.%Fe/40vol.% kaolin layer thickness is 1000 μ m, 65vol.%Fe/35vol.% kaolin layer thickness is 1000 μ m, 70vol.%Fe/30vol.% kaolin layer thickness is 1000 μ m, 75vol.%Fe/25vol.% kaolin layer thickness is 1000 μ m, 80vol.%Fe/20vol.% kaolin layer thickness is 1000 μ m, 85vol.%Fe/15vol.% kaolin layer thickness is 1000 μ m, 90vol.%Fe/10vol.% kaolin layer thickness is 1000 μ m, 95vol.%Fe/5vol.% kaolin layer thickness is 1000 μ m, 100vol.%Fe/0vol.% kaolin layer thickness is 1000 μ m, with above-mentioned green layer drying, obtain the different green compact of component volume percent content.With thickness is that the organic layer of 0.5mm is wrapped on the roll shaft of pair roller roll squeezer, the order of successively decreasing then by the kaolin percent by volume, with the green compact that make from the outside of this organic layer lamination parcel successively, and by pair roller roll squeezer roll-forming, make kaolin gradient composite pipe biscuit in the outer Fe/, in the roll-forming process, the control roll pressure pressure is 20MPa, and roll-in speed is 0.5cm/min; Afterwards, is it 1400 that this Fe/ kaolin gradient composite pipe biscuit is placed temperature? vacuum environment in the insulation 4 hours, make Fe/ kaolin gradient composite pipe.

Embodiment 5

Selecting particle diameter for use is the SiO of 0.1～50 μ m ₂Powder and particle diameter be the Ag powder of 0.1～50 μ m as raw material, preparation aperture 50mm, wall thickness 50mm, inwall are pure SiO ₂Layer, gradient transition ratio are that 30vol.%, outer wall are the multiple tube of pure Ag layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%Ag powder and 100vol.%SiO ₂Powder, 30vol.%Ag powder and 70vol.%SiO ₂Powder, 60vol.%Ag powder and 40vol.%SiO ₂Powder, 90vol.%Ag powder and 10vol.%SiO ₂Powder, 100vol.%Ag powder and 0vol.%SiO ₂Powder; The mixture of obtaining of respectively organizing is carried out planetary ball mill respectively and mixes, obtain the component percent by volume different respectively organize Ag/SiO ₂Mixed powder; With each group Ag/SiO ₂Mixed powder mixes with poly-vinyl alcohol solution and deionized water respectively, makes slurry respectively, in this slurry, percentage by volume, the metal/ceramic mixed powder is 50%, poly-vinyl alcohol solution is 10%, deionized water is 40%, with the vacuum degassing of sieving of this slurry, obtains casting slurry; Utilize the flow casting molding method, this casting slurry curtain coating is become thickness and multiple tube aperture, pipe thickness and the corresponding green layer of gradient transition ratio; The thickness of each green layer is respectively: 0vol.%Ag/100vol.%SiO ₂Layer thickness is 10mm, 30vol.%Ag/70vol.%SiO ₂Layer thickness is 10mm, 60vol.%Ag/40vol.%SiO ₂Layer thickness is 10mm, 90vol.%Ag/10vol.%SiO ₂Layer thickness is 10mm, 100vol.%Ag/0vol.%SiO ₂Layer thickness is 10mm, with above-mentioned green layer drying, obtains the different green compact of component volume percent content.With thickness is that the organic layer of 2mm is wrapped on the roll shaft of pair roller roll squeezer, presses SiO then ₂The order that percent by volume is successively decreased, with the green compact that make from the outside of this organic layer lamination parcel successively, by pair roller roll squeezer roll-forming, make the interior SiO of outer Ag/ ₂The gradient composite pipe biscuit, in the roll-forming process, the control roll pressure pressure is 25MPa, roll-in speed is 2cm/min, afterwards, should outer Ag/SiO ₂Is it 1150 that the gradient composite pipe biscuit places temperature? argon gas atmosphere in insulation 2.5 hours, make the interior SiO of outer Ag/ ₂Gradient composite pipe.

Embodiment 6

Select for use particle diameter be the SiC powder of 0.1～50 μ m and NiCr powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 30mm, wall thickness 35mm, inwall are that pure SiC layer, gradient transition ratio are that 20vol.%, outer wall are the multiple tube of pure NiCr layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%NiCr powder of mixture and 100vol.%SiC powder, 20vol.%NiCr powder and 80vol.%SiC powder, 40vol.%NiCr powder and 60vol.%SiC powder, 60vol.%NiCr powder and 40vol.%SiC powder, 80vol.%NiCr powder and 20vol.%SiC powder, 100vol.%NiCr powder and 0vol.%SiC powder; The mixture of obtaining of respectively organizing is carried out the planetary ball mill mixing respectively, obtain the different NiCr/SiC mixed powder of component percent by volume; Each group NiCr/SiC mixed powder is mixed with methocel solution and propyl alcohol respectively, make slurry respectively, in this slurry, percentage by volume, the NiCr/SiC mixed powder is 30%, methocel solution is 30%, propyl alcohol is 40%, with the vacuum degassing of sieving of this slurry, obtain casting slurry; Utilize the flow casting molding method, this casting slurry curtain coating is become thickness and multiple tube diameter, it is 5900 μ m that pipe thickness and the corresponding green layer of gradient transition ratio, the thickness of each green layer are respectively the 0vol.%NiCr/100vol.%SiC layer thickness, the 20vol.%NiCr/80vol.%SiC layer thickness is 5800 μ m, the 40vol.%NiCr/60vol.%SiC layer thickness is 5800 μ m, the 60vol.%NiCr/40vol.%SiC layer thickness is 5800 μ m, the 80vol.%NiCr/20vol.%SiC layer thickness is 5800 μ m, the 100vol.%NiCr/0vol.%SiC layer thickness is 5900 μ m powder; With above-mentioned green layer drying, obtain the different green compact of component volume percent content.With thickness is that the organic layer of 1.5mm is wrapped on the roll shaft of pair roller roll squeezer, the order of successively decreasing then by the SiC percent by volume, with the green compact that make from the outside of this organic layer lamination parcel successively, and by pair roller roll squeezer roll-forming, make SiC gradient composite pipe biscuit in the outer NiCr/, in the roll-forming process, the control roll pressure pressure is 5MPa, roll-in speed is 1cm/min, afterwards, should be to place temperature 1300 to SiC gradient composite pipe biscuit in outer NiCr/? vacuum environment in insulation 3 hours, make the interior SiC gradient composite pipe of outer NiCr/.

Embodiment 7

Selecting particle diameter for use is the Al of 0.1～50 μ m ₂O ₃Powder and particle diameter be the Ni powder of 0.1～50 μ m as raw material, preparation aperture 51mm, wall thickness 70mm, inwall are pure Al ₂O ₃Layer, gradient transition ratio are that 5vol.% and outer wall are the multiple tube of pure Ni layer.Get respectively percent by volume with embodiment 1 identical respectively organize each 100ml of mixture; And make green layer by the step of embodiment 1; The thickness of each green layer is respectively 0vol.%Ni/100vol.%Al ₂O ₃Layer thickness is 3340 μ m, 5vol.%Ni/95vol.%Al ₂O ₃Layer thickness is 3330 μ m, 10vol.%Ni/90vol.%Al ₂O ₃Layer thickness is 3330 μ m, 15vol.%Ni/85vol.%Al ₂O ₃Layer thickness is 3330 μ m20vol.%Ni/80vol.%Al ₂O ₃Layer thickness is 3330 μ m, 25vol.%Ni/75vol.%Al ₂O ₃Layer thickness is 3330 μ m, 30vol.%Ni/70vol.%Al ₂O ₃Layer thickness is 3330 μ m, 35vol.%Ni/65vol.%Al ₂O ₃Layer thickness is 3330 μ m, 40vol.%Ni/60vol.%Al ₂O ₃Layer thickness is 3330 μ m, 45vol.%Ni/55vol.%Al ₂O ₃Layer thickness is 3330 μ m, 50vol.%Ni/50vol.%Al ₂O ₃Layer thickness is 3330 μ m, 55vol.%Ni/45vol.%Al ₂O ₃Layer thickness is 3330 μ m, 60vol.%Ni/40vol.%Al ₂O ₃Layer thickness is 3330 μ m, 65vol.%Ni/35vol.%Al ₂O ₃Layer thickness is 3330 μ m, 70vol.%Ni/30vol.%Al ₂O ₃Layer thickness is 3330 μ m, 75vol.%Ni/25vol.%Al ₂O ₃Layer thickness is 3330 μ m, 80vol.%Ni/20vol.%Al ₂O ₃Layer thickness is 3330 μ m, 85vol.%Ni/15vol.%Al ₂O ₃Layer thickness is 3330 μ m, 90vol.%Ni/10vol.%Al ₂O ₃Layer thickness is 3330 μ m, 95vol.%Ni/5vol.%Al ₂O ₃Layer thickness is 3330 μ m, 100vol.%Ni/0vol.%Al ₂O ₃Layer thickness is 3330 μ m, with above-mentioned green layer, presses the method for embodiment 1, makes Al in the outer Ni/ ₂O ₃Gradient composite pipe.

Embodiment 8

Selecting particle diameter for use is the TiO of 0.1～50 μ m ₂Powder and particle diameter be the Cu powder of 0.1～50 μ m as raw material, preparation aperture 75mm, wall thickness 40mm, inwall are pure TiO ₂Layer, gradient transition ratio are that 25vol.%, outer wall are the multiple tube of pure Cu layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%Cu powder and 100vol.%TiO ₂Powder, 25vol.%Cu powder and 75vol.%TiO ₂Powder, 50vol.%Cu powder and 50vol.%TiO ₂Powder, 75vol.%Cu powder and 25vol.%TiO ₂Powder, 100vol.%Cu powder and 0vol.%TiO ₂Powder; The mixture of obtaining of respectively organizing is made green layer by the method identical with embodiment 2; The thickness of each green layer is respectively: 0vol.%Cu/100vol.%TiO ₂Layer thickness is 8000 μ m, 25vol.%Cu/75vol.%TiO ₂Layer thickness is 8000 μ m, 50vol.%Cu/50vol.%TiO ₂Layer thickness is 8000 μ m, 75vol.%Cu/25vol.%TiO ₂Layer thickness is 8000 μ m, 100vol.%Cu/0vol.%TiO ₂Layer thickness is 8000 μ m, with the method that above-mentioned green layer is pressed embodiment 2, makes TiO in the outer Cu/ ₂Gradient composite pipe.

Embodiment 9

Selecting particle diameter for use is the ZrO of 0.1～50 μ m ₂Powder and particle diameter be the SUS316L stainless steel powder of 0.1～50 μ m as raw material, preparation aperture 99mm, wall thickness 10mm, inwall are pure ZrO ₂Layer, gradient transition ratio are that 15vol.%, outer wall are the multiple tube of pure SUS316L stainless steel layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%SUS316L stainless steel powder/100vol.%ZrO of mixture ₂Powder, 15vol.%SUS316L stainless steel powder/85vol.%ZrO ₂Powder, 30vol.%SUS316L stainless steel powder/70vol.%ZrO ₂Powder, 45vol.%SUS316L stainless steel powder/55vol.%ZrO ₂Powder, 60vol.%SUS316L stainless steel powder/40vol.%ZrO ₂Powder, 75vol.%SUS316L stainless steel powder/25vol.%ZrO ₂Powder, 90vol.%SUS316L stainless steel powder/10vol.%ZrO ₂Powder, 100vol.%SUS316L stainless steel powder and 0vol.%ZrO ₂Powder; The mixture of obtaining of respectively organizing is made green layer by the method identical with embodiment 3 respectively, and the thickness of each green layer is respectively 0vol.%SUS316L stainless steel/100vol.%ZrO ₂Layer thickness is 1250 μ m, 15vol.%SUS316L stainless steel/85vol.%ZrO ₂Layer thickness is 1250 μ m, 30vol.%SUS316L stainless steel/70vol.%ZrO ₂Layer thickness is 1250 μ m, 45vol.%SUS316L stainless steel/55vol.%ZrO ₂Layer thickness is 1250 μ m, 60vol.%SUS316L stainless steel/40vol.%ZrO ₂Layer thickness is 1250 μ m, 75vol.%SUS316L stainless steel/25vol.%ZrO ₂Layer thickness is 1250 μ m, 90vol.%SUS316L stainless steel/10vol.%ZrO ₂Layer thickness is 1250 μ m, 100vol.%SUS316L stainless steel/0vol.%ZrO ₂Layer thickness is 1250 μ m powder; With above-mentioned green layer, press the method for embodiment 3, make outer SUS316L stainless steel/interior ZrO ₂Gradient composite pipe.

Embodiment 10

Select for use particle diameter be the kaolin powder of 0.1～50 μ m and Fe powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 99mm, wall thickness 100mm, inwall are that washed kaolin layer, gradient transition ratio are that 5vol.%, outer wall are the multiple tube of pure Fe layer.By the percent by volume identical with embodiment 4 get respectively total amount be respectively 100% respectively organize each 100ml of mixture; The mixture of obtaining of respectively organizing is made green layer by the method identical with embodiment 4; It is 5350 μ m that the thickness of each green layer is respectively 0vol.%Fe/100vol.% kaolin layer thickness, 5vol.%Fe/95vol.% kaolin layer thickness is 4700 μ m, 10vol.%Fe/90vol.% kaolin layer thickness is 4700 μ m, 15vol.%Fe/85vol.% kaolin layer thickness is 4700 μ m, 20vol.%Fe/80vol.% kaolin layer thickness is 4700 μ m, 25vol.%Fe/75vol.% kaolin layer thickness is 4700 μ m, 30vol.%Fe/70vol.% kaolin layer thickness is 4700 μ m, 35vol.%Fe/65vol.% kaolin layer thickness is 4700 μ m, 40vol.%Fe/60vol.% kaolin layer thickness is 4700 μ m, 45vol.%Fe/55vol.% kaolin layer thickness is 4700 μ m, 50vol.%Fe/50vol.% kaolin layer thickness is 4700 μ m, 55vol.%Fe/45vol.% kaolin layer thickness is 4700 μ m, 60vol.%Fe/40vol.% kaolin layer thickness is 4700 μ m, 65vol.%Fe/35vol.% kaolin layer thickness is 4700 μ m, 70vol.%Fe/30vol.% kaolin layer thickness is 4700 μ m, 75vol.%Fe/25vol.% kaolin layer thickness is 4700 μ m, 80vol.%Fe/20vol.% kaolin layer thickness is 4700 μ m, 85vol.%Fe/15vol.% kaolin layer thickness is 4700 μ m, 90vol.%Fe/10vol.% kaolin layer thickness is 4700 μ m, 95vol.%Fe/5vol.% kaolin layer thickness is 4700 μ m, 100vol.%Fe/0vol.% kaolin layer thickness is 5350 μ m, with the method that above-mentioned green layer is pressed embodiment 4, make kaolin gradient composite pipe in the outer Fe/.

Embodiment 11

Selecting particle diameter for use is the SiO of 0.1～50 μ m ₂Powder and particle diameter be the Ag powder of 0.1～50 μ m as raw material, preparation aperture 51mm, wall thickness 71mm, inwall are pure SiO ₂Layer, gradient transition ratio are that 40vol.%, outer wall are the multiple tube of pure Ag layer.By the percent by volume identical with embodiment 5, get respectively total amount be respectively 100% respectively organize each 100ml of mixture, and the mixture of respectively organizing that will obtain adopts the method identical with embodiment 5 to make green layer; The thickness of each green layer is respectively: 0vol.%Ag/100vol.%SiO ₂Layer thickness is 17750mm, 40vol.%Ag/60vol.%Si0 ₂Layer thickness is 17750mm, 80vol.%Ag/20vol.%SiO ₂Layer thickness is 17750mm, 100vol.%Ag/0vol.%SiO ₂Layer thickness is 17750mm, with the method that above-mentioned green layer is pressed embodiment 5, makes SiO in the outer Ag/ ₂Gradient composite pipe.

Embodiment 12

Select for use particle diameter be the SiC powder of 0.1～50 μ m and NiCr powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 75mm, wall thickness 85mm, inwall are that pure SiC layer, gradient transition ratio are that 20vol.%, outer wall are the multiple tube of pure NiCr layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%NiCr powder/100vol.%SiC powder of mixture, 20vol.%NiCr powder/80vol.%SiC powder, 40vol.%NiCr powder/60vol.%SiC powder, 60vol.%NiCr powder/40vol.%SiC powder, 80vol.%NiCr powder/20vol.%SiC powder, 100vol.%NiCr powder/0vol.%SiC powder; Respectively organize mixture with what obtain, method by embodiment 6 is made green layer, and it is that 14200 μ m, 20vol.%NiCr/80vol.%SiC layer thickness are that 14200 μ m, 40vol.%NiCr/60vol.%SiC layer thickness are that 14200 μ m, 60vol.%NiCr/40vol.%SiC layer thickness are that 14200 μ m, 80vol.%NiCr/20vol.%SiC layer thickness are that 14200 μ m, 100vol.%NiCr/0vol.%SiC layer thickness are 14000 μ m powder that the thickness of each green layer is respectively the 0vol.%NiCr/100vol.%SiC layer thickness; With the method that above-mentioned green layer is pressed embodiment 6, make SiC gradient composite pipe in the outer NiCr/.

Embodiment 13

Selecting particle diameter for use is the Al of 0.1～50 μ m ₂O ₃Powder and particle diameter be the Ni powder of 0.1～50 μ m as raw material, preparation aperture 100mm, wall thickness 100mm, inwall are pure Al ₂O ₃Layer, gradient transition ratio are that 5vol.% and outer wall are the multiple tube of pure Ni layer.Get respectively percent by volume with embodiment 1 identical respectively organize each 100ml of mixture; And make green layer by the step of embodiment 1; The thickness of each green layer is respectively 0vol.%Ni/100vol.%Al ₂O ₃Layer thickness is 5350 μ m, 5vol.%Ni/95vol.%Al ₂O ₃Layer thickness is 4700 μ m, 10vol.%Ni/90vol.%Al ₂O ₃Layer thickness is 4700 μ m, 15vol.%Ni/85vol.%Al ₂O ₃Layer thickness is 4700 μ m, 20vol.%Ni/80vol.%Al ₂O ₃Layer thickness is 4700 μ m, 25vol.%Ni/75vol.%Al ₂O ₃Layer thickness is 4700 μ m, 30vol.%Ni/70vol.%Al ₂O ₃Layer thickness is 4700 μ m, 35vol.%Ni/65vol.%Al ₂O ₃Layer thickness is 4700 μ m, 40vol.%Ni/60vol.%Al ₂O ₃Layer thickness is 4700 μ m, 45vol.%Ni/55vol.%Al ₂O ₃Layer thickness is 4700 μ m, 50vol.%Ni/50vol.%Al ₂O ₃Layer thickness is 4700 μ m, 55vol.%Ni/45vol.%Al ₂O ₃Layer thickness is 4700 μ m, 60vol.%Ni/40vol.%Al ₂O ₃Layer thickness is 4700 μ m, 65vol.%Ni/35vol.%Al ₂O ₃Layer thickness is 4700 μ m, 70vol.%Ni/30vol.%Al ₂O ₃Layer thickness is 4700 μ m, 75vol.%Ni/25vol.%Al ₂O ₃Layer thickness is 4700 μ m, 80vol.%Ni/20vol.%Al ₂O ₃Layer thickness is 4700 μ m, 85vol.%Ni/15vol.%Al ₂O ₃Layer thickness is 4700 μ m, 90vol.%Ni/10vol.%Al ₂O ₃Layer thickness is 4700 μ m, 95vol.%Ni/5vol.%Al ₂O ₃Layer thickness is 4700 μ m, 100vol.%Ni/0vol.%Al ₂O ₃Layer thickness is 5350 μ m, with above-mentioned green layer, presses the method for embodiment 1, makes Al in the outer Ni/ ₂O ₃Gradient composite pipe.

Embodiment 14

Selecting particle diameter for use is the TiO of 0.1～50 μ m ₂Powder and particle diameter be the Cu powder of 0.1～50 μ m as raw material, preparation aperture 200mm, wall thickness 60mm, inwall are pure TiO ₂Layer, gradient transition ratio are that 20vol.%, outer wall are the multiple tube of pure Cu layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%Cu powder and 100vol.%TiO ₂Powder, 20vol.%Cu powder and 80vol.%TiO ₂Powder, 40vol.%Cu powder and 60vol.%TiO ₂Powder, 60vol.%Cu powder and 40vol.%TiO ₂Powder, 80vol.%Cu powder and 20vol.%TiO ₂Powder, 100vol.%Cu powder and 0vol.%TiO ₂Powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 2; The thickness of each green layer is respectively: 0vol.%Cu/100vol.%TiO ₂Layer thickness is 10000 μ m, 20vol.%Cu/80vol.%TiO ₂Layer thickness is 10000 μ m, 40vol.%Cu/60vol.%TiO ₂Layer thickness is 10000 μ m, 60vol.%Cu/40vol.%TiO ₂Layer thickness is 10000 μ m, 80vol.%Cu/20vol.%TiO ₂Layer thickness is 10000 μ m, 100vol.%Cu/0vol.%TiO ₂Layer thickness is 10000 μ m, with the method that above-mentioned green layer is pressed embodiment 2, makes TiO in the outer Cu/ ₂Gradient composite pipe.

Embodiment 15

Selecting particle diameter for use is the ZrO of 0.1～50 μ m ₂Powder and particle diameter be the SUS316L stainless steel powder of 0.1～50 μ m as raw material, preparation aperture 150mm, wall thickness 20mm, inwall are pure ZrO ₂Layer, gradient transition ratio are that 30vol.%, outer wall are the multiple tube of pure SUS316L stainless steel layer.Get respectively following total amount be respectively 100% respectively organize mixture each 100ml:0vol.%SUS316L stainless steel powder and 100vol.%ZrO ₂Powder, 30vol.%SUS316L stainless steel powder and 70vol.%ZrO ₂Powder, 60vol.%SUS316L stainless steel powder and 40vol.%ZrO ₂Powder, 90vol.%SUS316L stainless steel powder and 10vol.%ZrO ₂Powder, 100vol.%SUS316L stainless steel powder and 0vol.%ZrO ₂Powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 3, and the thickness of each green layer is respectively 0vol.%SUS316L stainless steel/100vol.%ZrO ₂Layer thickness is 4000 μ m, 30vol.%SUS316L stainless steel/70vol.%ZrO ₂Layer thickness is 4000 μ m, 60vol.%SUS316L stainless steel/40vol.%ZrO ₂Layer thickness is 4000 μ m, 90vol.%SUS316L stainless steel/10vol.%ZrO ₂Layer thickness is 4000 μ m, 100vol.%SUS316L stainless steel/0vol.%ZrO ₂Layer thickness is 4000 μ m powder; With above-mentioned green layer, press the method for embodiment 3, make outer SUS316L stainless steel/interior ZrO ₂Gradient composite pipe.

Embodiment 16

Select for use particle diameter be the kaolin powder of 0.1～50 μ m and Fe powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 100mm, wall thickness 200mm, inwall are that washed kaolin layer, gradient transition ratio are that 5vol.%, outer wall are the multiple tube of pure Fe layer.By the percent by volume identical with embodiment 4 get respectively total amount be respectively 100% respectively organize each 100ml of mixture; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 4; It is 9750 μ m that the thickness of each green layer is respectively 0vol.%Fe/100vol.% kaolin layer thickness, 5vol.%Fe/95vol.% kaolin layer thickness is 9500 μ m, 10vol.%Fe/90vol.% kaolin layer thickness is 9500 μ m, 15vol.%Fe/85vol.% kaolin layer thickness is 9500 μ m, 20vol.%Fe/80vol.% kaolin layer thickness is 9500 μ m, 25vol.%Fe/75vol.% kaolin layer thickness is 9500 μ m, 30vol.%Fe/70vol.% kaolin layer thickness is 9500 μ m, 35vol.%Fe/65vol.% kaolin layer thickness is 9500 μ m, 40vol.%Fe/60vol.% kaolin layer thickness is 9500 μ m, 45vol.%Fe/55vol.% kaolin layer thickness is 9500 μ m, 50vol.%Fe/50vol.% kaolin layer thickness is 9500 μ m, 55vol.%Fe/45vol.% kaolin layer thickness is 9500 μ m, 60vol.%Fe/40vol.% kaolin layer thickness is 9500 μ m, 65vol.%Fe/35vol.% kaolin layer thickness is 9500 μ m, 70vol.%Fe/30vol.% kaolin layer thickness is 9500 μ m, 75vol.%Fe/25vol.% kaolin layer thickness is 9500 μ m, 80vol.%Fe/20vol.% kaolin layer thickness is 9500 μ m, 85vol.%Fe/15vol.% kaolin layer thickness is 9500 μ m, 90vol.%Fe/10vol.% kaolin layer thickness is 9500 μ m, 95vol.%Fe/5vol.% kaolin layer thickness is 9500 μ m, 100vol.%Fe/0vol.% kaolin layer thickness is 9750 μ m, with the method that above-mentioned green layer is pressed embodiment 4, make kaolin gradient composite pipe in the outer Fe/.

Embodiment 17

Selecting particle diameter for use is the SiO of 0.1～50 μ m ₂Powder and particle diameter be the Ag powder of 0.1～50 μ m as raw material, preparation aperture 200mm, wall thickness 101mm, inwall are pure SiO ₂Layer, gradient transition ratio are that 40vol.%, outer wall are the multiple tube of pure Ag layer.By the percent by volume identical with embodiment 5, get respectively total amount be respectively 100% respectively organize each 100ml of mixture, and the mixture of respectively organizing that will obtain adopts the method identical with embodiment 5 to make green layer; The thickness of each green layer is respectively: 0vol.%Ag/100vol.%SiO ₂Layer thickness is 25.25mm, 40vol.%Ag/60vol.%SiO ₂Layer thickness is 25.25mm, 80vol.%Ag/20vol.%SiO ₂Layer thickness is 25.25mm, 100vol.%Ag/0vol.%SiO ₂Layer thickness is 25.25mm, with the method that above-mentioned green layer is pressed embodiment 5, makes SiO in the outer Ag/ ₂Gradient composite pipe.

Embodiment 18

Select for use particle diameter be the SiC powder of 0.1～50 μ m and NiCr powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 150mm, wall thickness 150mm, inwall are that pure SiC layer, gradient transition ratio are that 20vol.%, outer wall are the multiple tube of pure NiCr layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%NiCr powder of mixture and 100vol.%SiC powder, 20vol.%NiCr powder and 80vol.%SiC powder, 40vol.%NiCr powder and 60vol.%SiC powder, 60vol.%NiCr powder and 40vol.%SiC powder, 80vol.%NiCr powder and 20vol.%SiC powder, 100vol.%NiCr powder and 0vol.%SiC powder; Respectively organize mixture with what obtain, method by embodiment 6 is made green layer, and it is that 25mm, 20vol.%NiCr/80vol.%SiC layer thickness are that 25mm, 40vol.%NiCr/60vol.%SiC layer thickness are that 25mm, 60vol.%NiCr/40vol.%SiC layer thickness are that 25mm, 80vol.%NiCr/20vol.%SiC layer thickness are that 25mm, 100vol.%NiCr/0vol.%SiC layer thickness are the 25mm powder that the thickness of each green layer is respectively the 0vol.%NiCr/100vol.%SiC layer thickness; With the method that above-mentioned green layer is pressed embodiment 6, make SiC gradient composite pipe in the outer NiCr/.

Embodiment 19

Selecting particle diameter for use is the Al of 0.1～50 μ m ₂O ₃Powder and particle diameter be the Ni powder of 0.1～50 μ m as raw material, preparation aperture 10mm, wall thickness 20mm, inwall are that pure Ni layer, gradient transition ratio are that 5vol.%, outer wall are pure Al ₂O ₃The multiple tube of layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%Al of mixture ₂O ₃Powder and 100vol.%Ni powder, 5vol.%Al ₂O ₃Powder and 95vol.%Ni powder, 10vol.%Al ₂O ₃Powder and 90vol.%Ni powder, 15vol.%Al ₂O ₃Powder and 85vol.%Ni powder, 20vol.%Al ₂O ₃Powder and 80vol.%Ni powder, 25vol.%Al ₂O ₃Powder and 75vol.%Ni powder, 30vol.%Al ₂O ₃Powder and 70vol.%Ni powder, 35vol.%Al ₂O ₃Powder and 65vol.%Ni powder, 40vol.%Al ₂O ₃Powder and 60vol.%Ni powder, 45vol.%Al ₂O ₃Powder and 55vol.%Ni powder, 50vol.%Al ₂O ₃Powder and 50vol.%Ni powder, 55vol.%Al ₂O ₃Powder and 45vol.%Ni powder, 60vol.%Al ₂O ₃Powder and 40vol.%Ni powder, 65vol.%Al ₂O ₃Powder and 35vol.%Ni powder, 70vol.%Al ₂O ₃Powder and 30vol.%Ni powder, 75vol.%Al ₂O ₃Powder and 25vol.%Ni powder, 80vol.%Al ₂O ₃Powder and 20vol.%Ni powder, 85vol.%Al ₂O ₃Powder and 15vol.%Ni powder, 90vol.%Al ₂O ₃Powder and 10vol.%Ni powder, 95vol.%Al ₂O ₃Powder and 5vol.%Ni powder, 100vol.%Al ₂O ₃Powder and 0vol.%Ni powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 1, and the thickness of each green layer is respectively 0vol.%Al ₂O ₃/ 100vol.%Ni layer thickness is 1000 μ m, 5vol.%Al ₂O ₃/ 95vol.%Ni layer thickness is 950 μ m, 10vol.%Al ₂O ₃/ 90vol.%Ni layer thickness is 950 μ m, 15vol.%Al ₂O ₃/ 85vol.%Ni layer thickness is 950 μ m, 20vol.%Al ₂O ₃/ 80vol.%Ni layer thickness is 950 μ m, 25vol.%Al ₂O ₃/ 75vol.%Ni layer thickness is 950 μ m, 30vol.%Al ₂O ₃/ 70vol.%Ni layer thickness is 950 μ m, 35vol.%Al ₂O ₃/ 65vol.%Ni layer thickness is 950 μ m, 40vol.%Al ₂O ₃/ 60vol.%Ni layer thickness is 950 μ m, 45vol.%Al ₂O ₃/ 55vol.%Ni layer thickness is 950 μ m, 50vol.%Al ₂O ₃/ 50vol.%Ni layer thickness is 950 μ m, 55vol.%Al ₂O ₃/ 45vol.%Ni layer thickness is 950 μ m, 60vol.%Al ₂O ₃/ 40vol.%Ni layer thickness is 950 μ m, 65vol.%Al ₂O ₃/ 35vol.%Ni layer thickness is 950 μ m, 70vol.%Al ₂O ₃/ 30vol.%Ni layer thickness is 950 μ m, 75vol.%Al ₂O ₃/ 25vol.%Ni layer thickness is 950 μ m, 80vol.%Al ₂O ₃/ 20vol.%Ni layer thickness is 950 μ m, 85vol.%Al ₂O ₃/ 15vol.%Ni layer thickness is 950 μ m, 90vol.%Al ₂O ₃/ 10vol.%Ni layer thickness is 950 μ m, 95vol.%Al ₂O ₃/ 5vol.%Ni layer thickness is 950 μ m, 100vol.%Al ₂O ₃/ 0vol.%Ni layer thickness is 950 μ m, with the method that above-mentioned green layer is pressed embodiment 1, and the outer Al of Ni/ in making ₂O ₃Gradient composite pipe.

Embodiment 20

Selecting particle diameter for use is the TiO of 0.1～50 μ m ₂Powder and particle diameter be the Cu powder of 0.1～50 μ m as raw material, preparation aperture 80mm, wall thickness 11mm, inwall are that pure Cu layer, gradient transition ratio are that 10vol.%, outer wall are pure TiO ₂The multiple tube of layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%TiO of mixture ₂Powder and 100vol.%Cu powder, 10vol.%TiO ₂Powder and 90vol.%Cu powder, 20vol.%TiO ₂Powder and 80vol.%Cu powder, 30vol.%TiO ₂Powder and 70vol.%Cu powder, 40vol.%TiO ₂Powder and 60vol.%Cu powder, 50vol.%TiO ₂Powder and 50vol.%Cu powder, 60vol.%TiO ₂Powder and 40vol.%Cu powder, 70vol.%TiO ₂Powder and 30vol.%Cu powder, 80vol.%TiO ₂Powder and 20vol.%Cu powder, 90vol.%TiO ₂Powder and 10vol.%Cu powder, 100vol.%TiO ₂Powder and 0vol.%Cu powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 2, and the thickness of each green layer is respectively: 0vol.%TiO ₂/ 100vol.%Cu layer thickness is 1mm, 10vol.%TiO ₂/ 90vol.%Cu layer thickness is 1mm, 20vol.%TiO ₂/ 80vol.%Cu layer thickness is 1mm, 30vol.%TiO ₂/ 70vol.%Cu layer thickness is 1mm, 40vol.%TiO ₂/ 60vol.%Cu layer thickness is 1mm, 50vol.%TiO ₂/ 50vol.%Cu layer thickness is 1mm, 60vol.%TiO ₂/ 40vol.%Cu layer thickness is 1mm, 70vol.%TiO ₂/ 30vol.%Cu layer thickness is 1mm, 80vol.%TiO ₂/ 20vol.%Cu layer thickness is 1mm, 90vol.%TiO ₂/ 10vol.%Cu layer thickness is 1mm, 100vol.%TiO ₂/ 0vol.%Cu layer thickness is 1mm, with the method that above-mentioned green layer is pressed embodiment 2, and the outer TiO of Cu/ in making ₂Gradient composite pipe.

Embodiment 21

Selecting particle diameter for use is the ZrO of 0.1～50 μ m ₂Powder and particle diameter be the SUS316L stainless steel powder of 0.1～50 μ m as raw material, preparation aperture 45mm, wall thickness 2mm, inwall be pure SUS316L stainless steel layer by layer, the gradient transition ratio is that 8vol.%, outer wall are pure ZrO ₂Multiple tube.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%ZrO of mixture ₂Powder and 100vol.%SUS316L stainless steel powder, 8vol.%ZrO ₂Powder and 92vol.%SUS316L stainless steel powder, 16vol.%ZrO ₂Powder and 84vol.%SUS316L stainless steel powder, 24vol.%ZrO ₂Powder and 76vol.%SUS316L stainless steel powder, 32vol.%ZrO ₂Powder and 68vol.%SUS316L stainless steel powder, 40vol.%ZrO ₂Powder and 60vol.%SUS316L stainless steel powder, 48vol.%ZrO ₂Powder and 52vol.%SUS316L stainless steel powder, 56vol.%ZrO ₂Powder and 44vol.%SUS316L stainless steel powder, 64vol.%ZrO ₂Powder and 36vol.%SUS316L stainless steel powder, 72vol.%ZrO ₂Powder and 28vol.%SUS316L stainless steel powder, 80vol.%ZrO ₂Powder and 20vol.%SUS316L stainless steel powder, 88vol.%ZrO ₂Powder and 12vol.%SUS316L stainless steel powder, 96vol.%ZrO ₂Powder and 4vol.%SUS316L stainless steel powder, 100vol.%ZrO ₂Powder and 0vol.%SUS316L stainless steel powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 3, and the thickness of each green layer is respectively 0vol.%ZrO ₂/ 100vol.%SUS316L stainless steel layer thickness is 140 μ m, 8vol.%ZrO ₂/ 92vol.%SUS316L stainless steel layer thickness is 140 μ m, 16vol.%ZrO ₂/ 84vol.%SUS316L stainless steel layer thickness is 140 μ m, 24vol.%ZrO ₂/ 76vol.%SUS316L stainless steel layer thickness is 140 μ m, 32vol.%ZrO ₂/ 68vol.%SUS316L stainless steel layer thickness is 140 μ m, 40vol.%ZrO ₂/ 60vol.%SUS316L stainless steel layer thickness is 140 μ m, 48vol.%ZrO ₂/ 52vol.%SUS316L stainless steel layer thickness is 140 μ m, 56vol.%ZrO ₂/ 44vol.%SUS316L stainless steel layer thickness is 140 μ m, 64vol.%ZrO ₂/ 36vol.%SUS316L stainless steel layer thickness is 140 μ m, 72vol.%ZrO ₂/ 28vol.%SUS316L stainless steel layer thickness is 140 μ m, 80vol.%ZrO ₂/ 20vol.%SUS316L stainless steel layer thickness is 140 μ m, 88vol.%ZrO ₂/ 12vol.%SUS316L stainless steel layer thickness is 140 μ m, 96vol.%ZrO ₂/ 4vol.%SUS316L stainless steel layer thickness is 140 μ m, 100vol.%ZrO ₂/ 0vol.%SUS316L stainless steel layer thickness is 180 μ m powder; With the method that above-mentioned green layer is pressed embodiment 3, SUS316L stainless steel in making/outer ZrO ₂Gradient composite pipe.

Embodiment 22

Select for use particle diameter be the kaolin powder of 0.1～50 μ m and Fe powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 10mm, wall thickness 50mm, inwall are that pure Fe layer, gradient transition ratio are that 5vol.%, outer wall are the multiple tube of washed kaolin layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.% kaolin powder of mixture and 100vol.%Fe powder, 5vol.% kaolin powder and 95vol.%Fe powder, 10vol.% kaolin powder and 90vol.%Fe powder, 15vol.% kaolin powder and 85vol.%Fe powder, 20vol.% kaolin powder and 80vol.%Fe powder, 25vol.% kaolin powder and 75vol.%Fe powder, 30vol.% kaolin powder and 70vol.%Fe powder, 35vol.% kaolin powder and 65vol.%Fe powder, 40vol.% kaolin powder and 60vol.%Fe powder, 45vol.% kaolin powder and 55vol.%Fe powder, 50vol.% kaolin powder and 50vol.%Fe powder, 55vol.% kaolin powder and 45vol.%Fe powder, 60vol.% kaolin powder and 40vol.%Fe powder, 65vol.% kaolin powder and 35vol.%Fe powder, 70vol.% kaolin powder and 30vol.%Fe powder, 75vol.% kaolin powder and 25vol.%Fe powder, 80vol.% kaolin powder and 20vol.%Fe powder, 85vol.% kaolin powder and 15vol.%Fe powder, 90vol.% kaolin powder and 10vol.%Fe powder, 95vol.% kaolin powder and 5vol.%Fe powder, 100vol.% kaolin powder and 0vol.%Fe powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 4; It is 2400 μ m that the thickness of each green layer is respectively 0vol.% kaolin/100vol.%Fe layer thickness, 5vol.% kaolin/95vol.%Fe layer thickness is 2380 μ m, 10vol.% kaolin/90vol.%Fe layer thickness is 2380 μ m, 15vol.% kaolin/85vol.%Fe layer thickness is that 2380 μ m 20vol.% kaolin/80vol.%Fe layer thicknesses are 2380 μ m, 25vol.% kaolin/75vol.%Fe layer thickness is 2380 μ m, 30vol.% kaolin/70vol.%Fe layer thickness is 2380 μ m, 35vol.% kaolin/65vol.%Fe layer thickness is 2380 μ m, 40vol.% kaolin/60vol.%Fe layer thickness is 2380 μ m, 45vol.% kaolin/55vol.%Fe layer thickness is 2380 μ m, 50vol.% kaolin/50vol.%Fe layer thickness is 2380 μ m, 55vol.% kaolin/45vol.%Fe layer thickness is 2380 μ m, 60vol.% kaolin/40vol.%Fe layer thickness is 2380 μ m, 65vol.% kaolin/35vol.%Fe layer thickness is 2380 μ m, 70vol.% kaolin/30vol.%Fe layer thickness is 2380 μ m, 75vol.% kaolin/25vol.%Fe layer thickness is 2380 μ m, 80vol.% kaolin/20vol.%Fe layer thickness is 2380 μ m, 85vol.% kaolin/15vol.%Fe layer thickness is 2380 μ m, 90vol.% kaolin/10vol.%Fe layer thickness is 2380 μ m, 95vol.% kaolin/5vol.%Fe layer thickness is 2380 μ m, 100vol.% kaolin/0vol.%Fe layer thickness is 2380 μ m, with the method that above-mentioned green layer is pressed embodiment 4, the outer kaolin gradient composite pipe of Fe/ in making.

Embodiment 23

Selecting particle diameter for use is the SiO of 0.1～50 μ m ₂Powder and particle diameter be the Ag powder of 0.1～50 μ m as raw material, preparation aperture 80mm, wall thickness 35mm, inwall are that pure Ag layer, gradient transition ratio are that 12vol.%, outer wall are pure SiO ₂The multiple tube of layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%SiO of mixture ₂Powder and 100vol.%Ag powder, 12vol.%SiO ₂Powder and 88vol.%Ag powder, 24vol.%SiO ₂Powder and 76vol.%Ag powder, 36vol.%SiO ₂Powder and 64vol.%Ag powder, 48vol.%SiO ₂Powder and 52vol.%Ag powder, 60vol.%SiO ₂Powder and 40vol.%Ag powder, 72vol.%SiO ₂Powder and 28vol.%Ag powder, 84vol.%SiO ₂Powder and 16vol.%Ag powder, 96vol.%SiO ₂Powder and 4vol.%Ag powder, 100vol.%SiO ₂Powder and 0vol.%Ag powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 5, and the thickness of each green layer is respectively: 0vol.%SiO ₂/ 100vol.%Ag layer thickness is 3500mm, 12vol.%SiO ₂/ 88vol.%Ag layer thickness is 3500mm, 24vol.%SiO ₂/ 76vol.%Ag layer thickness is 3500mm, 36vol.%SiO ₂/ 64vol.%Ag layer thickness is 3500mm, 48vol.%SiO ₂/ 52vol.%Ag layer thickness is 3500mm, 60vol.%SiO ₂/ 40vol.%Ag layer thickness is 3500mm, 72vol.%SiO ₂/ 28vol.%Ag layer thickness is 3500mm, 84vol.%SiO ₂/ 16vol.%Ag layer thickness is 3500mm, 96vol.%SiO ₂/ 4vol.%Ag layer thickness is 3500mm, 100vol.%SiO ₂/ 0vol.%Ag layer thickness is 3500mm, with the method that above-mentioned green layer is pressed embodiment 5, and the outer SiO of Ag/ in making ₂Gradient composite pipe.

Embodiment 24

Select for use particle diameter be the SiC powder of 0.1～50 μ m and NiCr powder that particle diameter is 0.1～50 μ m as raw material, preparation aperture 45mm, wall thickness 21mm, inwall are that NiCr layer, gradient transition ratio are that 20vol.%, outer wall are the multiple tube of pure SiC layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%SiC powder of mixture and 100vol.%NiCr powder, 20vol.%SiC powder and 80vol.%NiCr powder, 40vol.%SiC powder and 60vol.%NiCr powder, 60vol.%SiC powder and 40vol.%NiCr powder, 80vol.%SiC powder and 20vol.%NiCr powder, 100vol.%SiC powder and 0vol.%NiCr powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 6, and it is that 3500 μ m, 20vol.%SiC/80vol.%NiCr layer thickness are that 3500 μ m, 40vol.%SiC/60vol.%NiCr layer thickness 3500 μ m, 60vol.%SiC/40vol.%NiCr layer thickness are that 3500 μ m, 80vol.%SiC/20vol.%NiCr layer thickness are that 3500 μ m, 100vol.%SiC/0vol.%NiCr layer thickness are 3500 μ m that the thickness of each green layer is respectively the 0vol.%SiC/100vol.%NiCr layer thickness; With the method that above-mentioned green layer is pressed embodiment 6, the outer SiC gradient composite pipe of NiCr/ in making.

Embodiment 25

Selecting particle diameter for use is the Al of 0.1～50 μ m ₂O ₃Powder and particle diameter be the Ni powder of 0.1～50 μ m as raw material, preparation aperture 10mm, wall thickness 100mm, inwall are that pure Ni layer, gradient transition ratio are that 5vol.%, outer wall are pure Al ₂O ₃The multiple tube of layer.Get respectively percent by volume with embodiment 1 identical respectively organize each 100ml of mixture; And make green layer by the step of embodiment 1; The thickness of each green layer is respectively 0vol.%Al ₂O ₃/ 100vol.%Ni layer thickness is 4780 μ m, 5vol.%Al ₂O ₃/ 95vol.%Ni layer thickness is 4760 μ m, 10vol.%Al ₂O ₃/ 90vol.%Ni layer thickness is 4760 μ m, 15vol.%Al ₂O ₃/ 85vol.%Ni layer thickness is 4760 μ m20vol.%Al ₂O ₃/ 80vol.%Ni layer thickness is 4760 μ m, 25vol.%Al ₂O ₃/ 75vol.%Ni layer thickness is 4760 μ m, 30vol.%Al ₂O ₃/ 70vol.%Ni layer thickness is 4760 μ m, 35vol.%Al ₂O ₃/ 65vol.%Ni layer thickness is 4760 μ m, 40vol.%Al ₂O ₃/ 60vol.%Ni layer thickness is 4760 μ m, 45vol.%Al ₂O ₃/ 55vol.%Ni layer thickness is 4760 μ m, 50vol.%Al ₂O ₃/ 50vol.%Ni layer thickness is 4760 μ m, 55vol.%Al ₂O ₃/ 45vol.%Ni layer thickness is 4760 μ m, 60vol.%Al ₂O ₃/ 40vol.%Ni layer thickness is 4760 μ m, 65vol.%Al ₂O ₃/ 35vol.%Ni layer thickness is 4760 μ m, 70vol.%Al ₂O ₃/ 30vol.%Ni layer thickness is 4760 μ m, 75vol.%Al ₂O ₃/ 25vol.%Ni layer thickness is 4760 μ m, 80vol.%Al ₂O ₃/ 20vol.%Ni layer thickness is 4760 μ m, 85vol.%Al ₂O ₃/ 15vol.%Ni layer thickness is 4760 μ m, 90vol.%Al ₂O ₃/ 10vol.%Ni layer thickness is 4760 μ m, 95vol.%Al ₂O ₃/ 5vol.%Ni layer thickness is 4760 μ m, 100vol.%Al ₂O ₃/ 0vol.%Ni layer thickness is 4780 μ m, with above-mentioned green layer, presses the method for embodiment 1, the outer Al of Ni/ in making ₂O ₃Gradient composite pipe.

Embodiment 26

Selecting particle diameter for use is the TiO of 0.1～50 μ m ₂Powder and particle diameter be the Cu powder of 0.1～50 μ m as raw material, preparation aperture 80mm, wall thickness 75mm, inwall are that pure Cu layer, gradient transition ratio are that 15vol.%, outer wall are pure TiO ₂The multiple tube of layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%TiO of mixture ₂Powder/100vol.%Cu powder, 15vol.%TiO ₂Powder/85vol.%Cu powder, 30vol.%TiO ₂Powder/70vol.%Cu powder, 45vol.%TiO ₂Powder/55vol.%Cu powder, 60vol.%TiO ₂Powder/40vol.%Cu powder, 75vol.%TiO ₂Powder/25vol.%Cu powder, 90vol.%TiO ₂Powder/10vol.%Cu powder, 100vol.%TiO ₂Powder/0vol.%Cu powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 2, and the thickness of each green layer is respectively: 0vol.%TiO ₂/ 100vol.%Cu layer thickness is 9375 μ m, 15vol.%TiO ₂/ 85vol.%Cu layer thickness is 9375 μ m, 30vol.%TiO ₂/ 70vol.%Cu layer thickness is 9375 μ m, 45vol.%TiO ₂/ 55vol.%Cu layer thickness is 9375 μ m, 60vol.%TiO ₂/ 40vol.%Cu layer thickness is 9375 μ m, 75vol.%TiO ₂/ 25vol.%Cu layer thickness is 9375 μ m, 90vol.%TiO ₂/ 10vol.%Cu layer thickness is 9375 μ m, 100vol.%TiO ₂/ 0vol.%Cu layer thickness is 9375 μ m, with the method that above-mentioned green layer is pressed embodiment 2, and the outer TiO of Cu/ in making ₂Gradient composite pipe.

Embodiment 27

Selecting particle diameter for use is the ZrO of 0.1～50 μ m ₂Powder and particle diameter be the SUS316L stainless steel powder of 0.1～50 μ m as raw material, preparation aperture 45mm, wall thickness 51mm, inwall are that pure SUS316L stainless steel layer, gradient transition ratio are that 30vol.%, outer wall are pure ZrO ₂The multiple tube of layer.Get respectively following total amount be respectively 100% respectively organize each 100ml:0vol.%ZrO of mixture ₂Powder and 100vol.%SUS316L stainless steel powder, 30vol.%ZrO ₂Powder and 70vol.%SUS316L stainless steel powder, 60vol.%ZrO ₂Powder and 40vol.%SUS316L stainless steel powder, 90vol.%ZrO ₂Powder and 10vol.%SUS316L stainless steel powder, 100vol.%ZrO ₂Powder and 0vol.%SUS316L stainless steel powder; The mixture of obtaining of respectively organizing is made green layer by the method for embodiment 3 respectively, and the thickness of each green layer is respectively 0vol.%ZrO ₂/ 100vol.%SUS316L stainless steel layer thickness is 10200 μ m, 30vol.%ZrO ₂/ 70vol.%SUS316L stainless steel layer thickness is 10200 μ m, 60vol.%ZrO ₂/ 40vol.%SUS316L stainless steel layer thickness is 10200 μ m, 90vol.%ZrO ₂/ 10vol.%SUS316L stainless steel layer thickness is 10200 μ m, 100vol.%ZrO ₂/ 0vol.%SUS316L stainless steel layer thickness is 10200 μ m powder; With above-mentioned green layer, press the method for embodiment 3, SUS316L stainless steel in making/outer ZrO ₂Gradient composite pipe.

The inventive method can be controlled the gradient transition mode of aperture, pipe thickness and the pipe wall material of multiple tube, preparation process is simple, technology is controlled easily, the transition zone number of plies and the thickness of the metal and ceramic gradient composite pipe that makes are unrestricted, have good wearability, chemical stability and thermal shock resistance, can be applicable in the field of high temperature resistant, the wear-resistant and heat shock resistance structural material of many needs.

Claims

1. the preparation method of metal and ceramic gradient composite pipe, it is characterized in that, this method combines doctor-blade casting process and pair roller roll-in technology, making inwall is that pure ceramic layer, gradient transition are the metal/ceramic multiple tube biscuit of simple metal layer to outer wall, then, with this multiple tube biscuit sintering curing, making inwall is that pure ceramic outer wall is the metal and ceramic gradient composite pipe of simple metal, specifically carries out according to the following steps:

The aperture D of metal/ceramic multiple tube is 10mm≤D≤50mm,

The aperture D of metal/ceramic multiple tube is 50mm＜D＜100mm,

When 1. the thickness of pipe wall H of metal/ceramic multiple tube was 10mm≤H≤70mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤25vol.%,

2. the thickness of pipe wall H of metal/ceramic multiple tube is 70mm＜H≤100mm, and the transition ratio Φ of gradient transitional lay is 5vol.%≤Φ≤40vol.%;

The aperture D of metal/ceramic multiple tube is 100mm≤D≤200mm,

When 1. the thickness of pipe wall H of metal/ceramic multiple tube was 20mm≤H≤100mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤30vol.%,

When 2. the thickness of pipe wall H of metal/ceramic multiple tube was 100mm＜H≤200mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤40vol.%;

When the aperture of metal/ceramic multiple tube D is that 100mm≤D≤200mm, thickness of pipe wall H are the transition ratio Φ of 20mm≤H≤100mm and gradient transitional lay when being 5vol.%≤Φ≤30vol.%, the thickness S of each gradient transitional lay is 0.5mm≤S≤0.25H,

2. according to the described preparation method of claim 1, it is characterized in that the adhesive in the described step 3 adopts polyvinyl butyral solution, poly-vinyl alcohol solution or methocel solution.

3. according to the described preparation method of claim 1, it is characterized in that the solvent in the described step 3 adopts the isomer of ethanol, propyl alcohol, butanols, amylalcohol, deionized water or toluene or above-mentioned each solvent.

4. according to the described preparation method of claim 1, it is characterized in that in the roll-forming process in the described step 5, roll-in pressure is 5MPa～30MPa, roll-in speed is 0.5cm/min～2cm/min.

5. the preparation method of metal and ceramic gradient composite pipe, it is characterized in that, doctor-blade casting process and pair roller roll-in technology are combined, making inwall is that simple metal layer, gradient transition are the metal/ceramic multiple tube biscuit of pure ceramic layer to outer wall, then, with this multiple tube biscuit sintering curing, make inwall for the simple metal outer wall is the metal and ceramic gradient composite pipe of pure pottery, specifically carry out according to the following steps:

The aperture D of metal/ceramic multiple tube is 10mm≤D≤80mm,

When 3. the thickness of pipe wall H of metal/ceramic multiple tube was 50mm＜H≤100mm, the transition ratio Φ of gradient transitional lay was 5vol.%≤Φ≤30vol.%:

6. according to the described preparation method of claim 5, it is characterized in that the adhesive in the described step 3 adopts polyvinyl butyral solution, poly-vinyl alcohol solution or methocel solution.

7. according to the described preparation method of claim 5, it is characterized in that the solvent in the described step 3 adopts the isomer of ethanol, propyl alcohol, butanols, amylalcohol, deionized water or toluene or above-mentioned each solvent.

8. according to the described preparation method of claim 5, it is characterized in that in the roll-forming process in the described step 5, roll-in pressure is 5MPa～30MPa, roll-in speed is 0.5cm/min～2cm/min.