WO2007140714A1

WO2007140714A1 - High throughput method and device for characterizing membrane

Info

Publication number: WO2007140714A1
Application number: PCT/CN2007/001752
Authority: WO
Inventors: Zhuo Wang; Youqi Wang
Original assignee: Accelergy Shanghai R & D Center Co., Ltd.; Accelergy Corporation
Priority date: 2006-06-01
Filing date: 2007-06-01
Publication date: 2007-12-13

Abstract

A high throughput method and device for characterizing a membrane (151). The method comprises the following steps: 1) placing a membrane (151) to be characterized with two or more samples (152) thereof on an opening of a first container (150) to form an enclosed first chamber, wherein the first side of the membrane faces the first chamber; 2) filling the first chamber with one or more predetermined gases; 3) placing a probe (160) over and close to the second side of the membrane to collect gaseous substance above the samples (152); 4) analyzing the collected gaseous substance to determine the property of the samples (152).

Description

High Throughput Method and Device for Characterizing Membrane

FIELD OF THE INVENTION

[01] The present invention relates to a high throughput method and device for characterizing membrane.

BACKGROUND OF THE INVENTION

[02] With the development of the materials science, inorganic functional membranes such as oxygen permeable membrane, hydrogen permeable membrane play more and more important roles in the separating process of the energy field.

[03] Take the oxygen permeable membrane for example, as an inorganic functional membrane that can simultaneously transfer oxygen ion and electron, it not only can selectively permit oxygen passing through under medium temperature and high temperature, but also has an additional catalyzing function to some extent, this makes it have a broad application prospect in the fields of solid oxide fuel cell, oxygen sensor, oxygen separator and conversion of natural gas, in particular, the application of providing oxygen on conversion of natural gas.

[04] The conversion of natural gas means that the natural gas is converted to liquid fuel or other chemical products etc. by a serial of treatment, thus the utilization ratio of the natural gas can be increased. Generally, the conversion of natural gas comprises two stages:^* the first stage, wherein the natural gas is converted to syngas through indirect conversion process; the second stage, wherein the syngas is converted to the liquid fuels or other chemical products through Fischer-Tropsch synthesis. And during the first stage of the syngas preparation, huge energy is needed to maintain the endothermic reaction during the whole process if the traditional process such as steam reforming process is used; and huge amount of pure oxygen is needed if the novel process, such as partial oxidation process and combined reforming process is used. At present, the mass production of oxygen either consumes huge energy, such as low temperature separation process; or runs with low efficiency and small scale, such as pressure swing adsorption process. Thus, the technical problem in the first stage of preparation of syngas renders the cost of this stage accounting for about 60% of the whole cost, and also maintains the whole cost of the conversion of the natural gas in a high level, thus stunt the large-scale industrialization of the conversion of the natural gas. [05] However, the above mentioned problems can be solved by combination of the oxygen permeable membrane with the methane partial oxidation/combined reforming process, wherein the preparation of oxygen and syngas can be performed in a same reactor, resulting in the cost thereof being greatly reduced. Additionally, the oxygen permeable membrane can be used in oxygen-rich catalyzing burning to increase the stability of flame and decrease the discharging of the NO_x and CO. Further, whether the oxygen permeable membrane can be actually used in large-scale in the conversion of the natural gas, at one hand it depends on its sufficient oxygen permeability to reach a given production efficiency; on the other hand it depends on its sufficient mechanical strength so that it can resist the stress cracking and the creep deformation from the pressure difference between the two sides of the membrane.

[06] The oxygen permeability and the mechanical strength of the oxygen permeable membrane greatly depend on the element component of the material, thickness of the membrane, composite structure of the membrane or surface activity of the membrane, etc.

[07] The original oxygen ion conducting material is a series of oxide of YSZ (yttria stabilized oxide zirconia). The materials have high conductivity of oxygen ion, but the electron conductivity thereof is extremely low. Thus, an external circuit is needed to complement the charge, but this complicates the equipment, and it is difficult to connect the external circuit under high temperature. Additionally, the conduct of electrons is concentrate at the joint of a wire and the membrane so that the conduction of the oxygen ion is uneven. So, this kind of membrane fails to meet the requirements.

[08] The oxygen permeable oxide membrane with perovskite structure disclosed by Teraoka et al. in 1985 has a very high oxygen permeability, then much more attention is attracted to perovskite and the materials with corresponding structure, and they are considered to be the most potential candidate materials for the oxygen permeable membrane. The oxygen permeable membrane with perovskite and corresponding structure is a mixed ion oxygen permeable membrane, which not only can transfer the oxygen ion through its oxygen cavity, and but also can transfer the electron by utilizing the valence variable property of the valence variable metal. Thus, it has the conductivity property of both oxygen ions and electrons so that the transfer efficiency of oxygen ion is highly increased.

[09] Further, based on the disclosure of Teraoka, U.S. Pat. Pub. No. 20030218991 discloses an oxygen permeable membrane constituted by elements of La, Sr, Fe, Cr, O, which can achieve an oxygen flux of 13 to 16 sccm/cm² under a designated condition. U.S. Pat. No. 5,723,074 also discloses an oxygen permeable membrane with a structure of SrFeCo_0.5θ_x, which can achieve an oxygen flux of 1.8~4.6 sccm/cm². U.S. Pat. No. 6,638,575 discloses an oxygen permeable membrane with a structure of La_o.o₅ Sr_o.95 CoO_3-d, which can achieve an oxygen flux of 9.0 sccm/cm². U.S. Pat. Pub. No. 20050061663 discloses an oxygen permeable membrane constituted by mixing system of LSFT (an oxide constituted by the elements of La, Sr, Co, Fe etc.) and CGO (an oxide constituted by the elements of Ce, Gd etc.), which can achieve an oxygen flux of 15.6 sccm/cm² at 1000°C. CN Pat. No. 1416946 discloses an oxygen permeable membrane with a structure of Ba_o.5 Sr₀.5Cθo.8θ_3-d, which can achieve an oxygen flux of 11.5 sccm/cm .

[10] The embodiments of some oxygen permeable membranes with different structures are discussed above. As the oxygen permeability of the oxygen permeable membrane with perovskite and corresponding structure has an important relationship with its constituted elements and contents thereof, the materials with different constituted elements present big differences in their oxygen permeability. And at present, 90% of the elements listed in the Elements Periodic Table can be used to form the perovskite and corresponding structure, and the same structure can be formed by different elements and different content of the elements. And by now, the regular relationship between the elements and its properties is still not found in the research and development of the elements that constitute the materials of theses oxygen permeable membranes with high oxygen flux and the content thereof. While, if the traditional method is used to test each of the elements one by one, the time and the sources consumed will be unimaginable.

[11] Further, for the thickness factor, based on the classic Wagner theory (for details, please refer to Bouwmeester, H.J.M., Dense ceramic membranes for methane conversion. Catalysis Today, 2003. 82(1-4): p. 141-150), the oxygen flux is almost inversely proportional to the thickness when the influence of the surface of the membrane is small, so decreasing of the thickness of the membrane can increase the oxygen flux. Also, US Pat. No. 6,332,964 discloses that the oxygen flux increases from 1.8sccm/cm² to 4.0sccm/cm² as the thickness of the membrane constituted by La_0.o5Sro_.95Co0_3-d decreases from lmm to 0.3mm.

[12] Further, the composite structure factor of the oxygen permeable membrane has an important influence on the integrated property of the oxygen permeability and mechanical property. For the above mentioned oxygen permeable membrane with single layer structure, decreasing the thickness of the oxygen permeable membrane -A- can increase the oxygen flux to some extent, but the mechanical strength of the membrane decreases correspondingly. When the oxygen permeable membrane is used in syngas preparation by partial oxidation of the methane, conventionally a high pressure ( 20-30bar ) is used in one side of the oxygen permeable membrane and a pressure of about atmosphere pressure is used in the other side of the oxygen permeable membrane with the consideration of the production efficiency and the down stream F-T synthesis so that a big pressure difference between two sides of the oxygen permeable membrane is rendered, therefore, a high level mechanical strength of the oxygen permeable membrane is required. It can be seen that, the oxygen permeable membrane with single layer structure can not meet the requirement of both oxygen permeability and the mechanical strength being necessary.

[13] In 1989, Teraoka et al. reported an oxygen permeable membrane with composite structure, which is widely used later. The composite structure comprises a porous support layer and a dense layer, wherein the support layer provides the mechanical strength, and the dense layer (can be constituted by above-mentioned oxides with perovskite structure) provides the oxygen permeability. Since the dense layer can be made relatively thinner and the support layer can be made relatively thicker, such oxygen permeable membrane has high oxygen flux and high mechanical strength simultaneously. Additionally, the composite structure can also promote the oxygen permeation function of the oxygen permeable membrane.

[14] US Pat. No. 5,240,480 discloses many oxygen permeable membranes with composite structure, and it finds that the oxygen flux is considerably increased by the composite structure through simulation calculation of oxygen flux to these different composite structures. For example, the oxygen permeation flux is considerably increased when the support layer is an active material, so that the thickness thereof is not very important. The pore size of the support layer also affects the oxygen flux, wherein the oxygen flux decreases as the pore size increases.

[15] Additionally, US Pat. No. 6,165,553 also discloses an oxygen permeable membrane, and also investigates the influences of the thickness of the dense layer, porosity of the porous support layer and the nanocrystalline surface to the oxygen flux. Wherein, the oxygen flux of the oxygen permeable membrane increases from about lsccm/cm to 16.6sccm/cm as the thickness of the dense layer decreases from 1.0 mm to 0.5 mm even to 2 μm. The oxygen flux of the oxygen permeable membrane increases by 6-12% as the porosity of the porous layer increases from 25% to 32%. The oxygen exchange rate of membrane surface increases by 4 to 5 times when the dense layer is provided with a layer of nano-crystalline film of the same LSCF material.

[16] It can be seen that, the structures and combination manner of the dense layer and the porous support layer have much influence on the oxygen permeability of the oxygen permeable membrane. However, at present, there are still very short of research on the structure of the oxygen permeable membrane, and so lacks the experiment validate.

[17] Further, the surface activity factor of the oxygen permeable membrane works until the thickness of the oxygen permeable membrane reduces to a certain extent. At that time continue reducing the thickness of the membrane does not affect the oxygen flux, but the oxygen flux can be further enhanced by modifying the surface of the membrane. Further, it was reported that the oxygen flux of the oxygen permeable membrane is somewhat enhanced after the roughness treatment, surface activity treatment, etc. of its surface facing to the low pressure oxygen. For example, U.S. Pat. No. 6,264,811 discloses a method of treating the surface by chemical etching, and the oxygen flux of membranes of its examples increased from 1.9 sccm/cm² to 4.3 sccm/cm².

[18] In a nutshell, since the oxygen permeability of the oxygen permeable membrane depends on many factors such as of elements component, thickness of the membrane, composite structure, and surface activity of the membrane etc., a number of experiments is needed to synthesis and characterize these oxygen permeable membrane samples with different structures. The suitable structure only can be selected in this manner. But by now, there is still no high throughput method for synthesizing and characterizing membrane samples. Although U.S. Pat. Pub. No.20030100120 discloses a high throughput method for testing the catalysts; it is not suitable for characterizing the membrane samples.

[19] There is an urgent requirement of a method for preparation and characterization of a number of membrane samples in the industry, so as to perform large numbers of experiments to obtain adequate experimental data, and select a structure of the oxygen permeable membrane that is suitable for industrial application accordingly to solve the bottleneck problem in industrial application of the oxygen permeable membrane.

[20] At the same time, the research on the composite structure still limits to the support layer, such as, the researches on the number of layers, the class of the materials used, the thickness and the pore size etc. And the dense layer of the oxygen permeable membrane still uses single layer structure. But different materials vary in the capacities of oxygen ion transportation and surface exchanging. So, the industry also needs to broad its concept of research on composite structure, instead of limiting to the support layer.

SUMMARY OF THE INVENTION

[21] In one aspect, the present invention provides a membrane comprising two or more samples thereon, and each sample comprises one or more supporting layers and one or more dense layers provided thereon. Further, any known materials in the art for a support layer and dense layer can be used as the materials constituted the support layer and the dense layer of the samples of the membrane of the present invention.

[22] For example, the structure of the dense layer of the oxygen permeable membrane can be presented by formula: A_xB_yO₂, wherein A comprises one or more elements selected from the group consisting of IA elements family, HA elements family and IIIA elements family; B comprises one or more elements selected from the group consisting of IVA elements family, VA elements family, VIA elements family, VIIA elements family, VIIIA elements family, IB elements family, HB elements family, IIIB elements family, IVB elements family, VB elements family; O means oxygen; and the sub-coefficient: x, y, z varies based on the specific elemental component.

[23] Further, since there is no limitation on the specific number of the elements contained in A and B, the formula A_xB_yO_z can deduce to a plurality of embodiments, such as: Al_xlA2_x2B_yO_z, A_xBl_ylB2_y2B3_y3O_z, Al_xlA2_x2Bl_yiB2_y2O_z, Al_xlA2_x2Bl_ylB2_y2 B3_y3O_z, Al_xlA2χ₂ ...An_xnBl_ylB2_y2... Bn_7nO₂ etc; wherein "n" is any natural number. Specifically, it can be Lao.₆Sr₀.₄Co0_3-z, Lao.gSro.₂Co0₃._z, La₀.₇Sro.₃Ga₀.₆Fe_0.40₃, La_0.2 Sr_0-8CoO_3-25 LaO_-2SrO₁₈FeCsCOc₁Cr_C1O_3-S, Lao.6Sr₀.₄Co0_3-z, Bao.₅Sro.5Cθo.₈Feo.₂0_3-δ₅ Sr Co₀.₈Fe₀.₂O₃ etc. And a skilled in the art can develop other formulae based on the formulae disclosed above, which are obvious to the present invention and do not go beyond the protecting scope of the present invention.

[24] And the specific number of the multilayer dense layers can be 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 10 layers, more than ten layers, tens layers, hundreds layers etc. depended on the specific embodiment but not limited thereto. The component of each layer in the two layers or multilayer can follow the above-mentioned formulae. For example, the two layers structure can be: La_0-7Sr_0-3Ga_C6Fe_0-4O₃ + La_0-6Sr_0-4CoO_3-Z, La_0-2Sr_0-8Fe_0-8Co_0-1CrO_-1O_3-5 + La_0-6Sr_0-4CoO_3-2, Ba₀₅Sr_O-SCo_0-8Fe_{O 2}O_3-S + SrCo_0-8Fe_0-2O₃; the three layers structure can be: La_0-2Sr_0-8 Cθo_-9Fe_{0 1}θ_3-z+Lao.₂Sr₀.₈Co0₃-_z+Lao_-3Sro.₇Co0_3-z; the four layers structure can be: La_0-2. Sr_0-8Co_0-8Fe_0-2O_3-2 +La_C2Sr_0-8Co_0-9Fe_0-1O_3-Z +La_0-2Sr_0-8CoO_3-2 +La_0-3Sr_0-7CoO_3-2; the four layers structure can be: La_0-2Sr_0-8Co_0-8Fe_0-2O_3-Z+ La_0-2Sr_0-8Co_0-9Fe_0-1 O_3-Z+ La_0-2Sr_0-8Co O_3-2+ La₀,₃Sro_-7Co0₃__z; the five layers structure can be: La₀.₂Sr₀.₈Cθo,₉Fe_0-10_3-z+ La^_-2 Sr_0-8CoO_3-Z + La_C3Sr_0-7CoO_3-2 + La_0-4Sr_0-6CoO_3-2 + La_0-SSr_0-5CoO_3-2; the seven layers structure can be: La_O-2Sr_0-8Co_0-SFe_0-2O_3-2 + La_0-2Sr_O-8Co_0-9Fe_O-1O_3-2 + La_0-2Sr_0-8COO_3-2 + La_0-3Src₇Co0_3-z+La_0-4Sr_0-6Co0_3-z+La_0-5Sro_-5Co0₃._z+La_0-6Sr_0-4Co0_3-z.

[25] The materials of the dense layer of hydrogen permeable membrane sample comprise Pd, Yt, Ru, Ce, Cu, Pd alloys etc, wherein the Pd alloys comprise Pd-Yt alloy, Pd-Ru alloy, Pd-Ce alloy, Pd-Cu alloy etc. with the content ratio of the elements in the alloy can be adjusted as required.

[26] The materials constituted the support layer of each membrane sample usually are gas-passing porous materials, such as inert inorganic material, mixed ion conducting material, high temperature resistant alloy, heating resistant ceramic and heating resistant molecule sieve etc. Specifically, it can be Al₂O₃, SiO₂, MgO, TiO₂, LSCO, YSZ, CGO and perovskite structure: La^_xS^Co^_yFe_y 0_3-d, etc. The support layer generally support the membrane to increase its mechanical strength, but not necessarily take part in the function of the membrane itself, such as gas permeation function.

[27] Further, if the support layer (supporter) comprises two or more layers, for example, constituted by the porous materials, the pore structure of the material of each layer is different. In one embodiment, with reference to Fig. 1, supporter 10 comprises several layers 11, 12, 13, and the pore size 111, 121, 131 of the porous materials constituted different layers are different.

[28] Further, if supporter comprises two or more layers, i.e., the supporter structure comprises bottom layer, top layer, and one or more intermediate layers possibly existed therebetween, the bottom layer can be porous material with bigger pore size and connected pores with the pore size preferably varies from 100 nm to 100 μm, so as to provide the necessary strength to the whole membrane sample and to reduce the resistance to the transport of the gas (such as, oxygen). The material for the bottom layer comprises heat resistant inert inorganic material, active mixed ion conducting material, oxygen ion conducting material, high temperature resistant alloy, heating resistant ceramic etc; specifically, it can be Al₂O₃, SiO₂, MgO, TiO₂, LSCO, YSZ and CGO etc. The top layer of the supporter can be a structure with smaller pore size preferably in the range of from lnm to lOOnm, and the pores can be connected with each other or be apart from each other, which provides optimal condition for the contact between the dense layer and the gas molecule or the converting of the gas molecule to gas ion (such as, the converting of oxygen molecule to oxygen ion). In different embodiments, please refer to Figs. 2 and 3, the pores 21, 31 of the top layers 20, 30 of the supporter are apart from each other and connected with each other respectively. The materials for the top layer of the supporter comprises oxygen ion conducting material, mixed ion conducting material, heating resistant molecule sieve etc., specifically it can be YSZ, perovskite structure (the formula thereof can be La_1-xSr_xCo_1-yFe_yO_3-d)etc. Further, the pore size of the bottom layer, intermediate layer, and top layer preferably follow the rules of from big to small, i.e., the pore size of the bottom layer is the biggest, the pore size of the intermediate layer is smaller, and the pore size of the top layer is the smallest. Further, in a different embodiment, the materials selected for the bottom layer, intermediate layer and top layer of the supporter preferably match with each other in the aspects of coefficient of thermal expansion, pore size and pore structure.

[29] In another aspect, the present invention provides a high throughput method of preparation a membrane with two or more samples thereof in accordance with the present invention, comprising the following steps:

[30] firstly, a substrate is provided;

[31] secondly, two or more samples are formed on the substrate, and each sample comprises one or more support layers and one or more dense layers thereon.

[32] Further, the method of producing the samples on a substrate to form the membrane in accordance with the present invention can be any known methods in the art, such as high throughput deposition method. In details, the deposition technology comprises physical vapor deposition (PVD) and chemical vapor deposition (CVD), wherein the physical vapor deposition (PVD) is a technology of depositing desired element membrane layer on the surface of the substrate by a physical process of heating evaporation, glow discharge and arc discharge etc; and in different embodiments, it comprises ion plating, sputtering, plasma spraying etc. The CVD is a film deposition technology that produces solid products from reactant/reactants (usually gas/gases) by using chemical reaction in a reactor, which in turn is deposited on the surface of the substrate; in different embodiments, it comprises atmospheric pressure chemical vapor deposition (APCVD), low-pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), metal organic chemical vapor deposition (MOCVD), ultra-high vacuum chemical vapor deposition (UHV-CVD), electron cycltron resonance chemical vapor deposition (ECR-CVD), electrochemical vapor deposition (EVD), etc. Further, the deposition technology will not be explained in detail, as it is the known technology in the art.

[33] Further, the manner of performing the deposition technology comprises the manner of deposition in sequence and the manner of deposition in parallel. The manner of deposition in sequence means that only one region is deposited per time; while the manner of deposition in parallel means that at least two or more regions are deposited simultaneously, wherein the number of the regions deposited simultaneously depends on the specific application and is not limited in any way. The manner of deposition in sequence and deposition in parallel will be explained with reference to different embodiments.

[34] In an embodiment using the manner of deposition in sequence, with reference to Fig. 4, two samples 41, 42 are formed one by one on a substrate 40. In other embodiments, samples 41, 42 can also be formed simultaneously. Further, since many times deposition of different structures and materials are needed to form a sample, the manner of deposition in sequence comprises: (A) membrane samples are deposited in sequence, i.e. the deposition of the second membrane is started after the completion of the first one; (B) the same structure of the membrane samples are deposited in sequence, i.e. the same structure of the different membrane samples are deposited in sequence as the different membrane samples may have some identical component structure.

[35] The flow chart of an embodiment using the manner of deposition in sequence is shown in Fig.5. Firstly, the structure/material "E" of the first membrane sample is deposited on the first region 51 of the substrate 50; secondly, the structure/material "E" of the second membrane sample is deposited on the second region 52; thirdly, the structure/material "F" of the first membrane sample is deposited on the first region 51; fourthly, the structure/material "G" of the second membrane sample is deposited on the second region 52. In other embodiments, the deposition of the structure/material "E", "G" in second region 52 is started after the completion of the deposition of structure/material "E", "F" in the first region 51.

[36] The flow chart of an embodiment using the manner of deposition in parallel is as shown in Fig.6. Firstly, the structure/material "H" of the first and third membrane samples are deposited on the first and third regions 61, 63 of the substrate 60; secondly, the structure/material "I" of the first and second membrane samples are deposited on the first and second regions 61, 62 of the substrate 60; thirdly, the structure/material "J" of the second and third membrane samples are deposited on the second and third regions 62, 63 of the substrate 60.

[37] The above-mentioned two manners of deposition can be implemented in a combined way. The flow chart of an embodiment using the combination of two manners is as shown in Fig.7. Firstly, the structure/material "K" of the first membrane sample is deposited on the first region 71 of the substrate 70; secondly, the structure/material "L" of the second and third membrane samples are deposited on the second and third regions 72, 73; thirdly, the structure/material "M" of the first and second membrane samples are deposited on the first and second regions 71, 72, simultaneously the structure/material "N" of the third membrane sample is deposited on the third region 73.

[38] Further, in the embodiments mentioned above, the structures/materials: "E", "F", "G", "H", "I", "J", "K", "L", "M", "N" of the deposition formed membrane samples can be either the constituted parts of the membrane samples, such as a supporting layer or a dense layer, or the constituted part of the supporting layer or dense layer.

[39] Further, for the substrate, it can be a part of membrane, or not. If it is a part of the membrane, it usually serves as a supporting layer of the samples disposed on the membrane. So during the process of production, the material suitable for supporting layer of the membrane samples can be directly selected as the material for the substrate to simplify the process of production. Specifically, the material for the substrate can be the material disclosed by herein or the material known in the art. Further if the substrate does not serve as the supporting layer of the samples of the membrane, it will only serve as a carrier of the membrane, the method of forming the supporting layer on the substrate can be any method known in the art, such as process of pore-forming by powder, liquid phase process (such as, sol-gel process, suspension spin coating deposition process), sputtering process, pulsed laser deposition, etc.

[40] Further, the membrane samples formed on one same substrate can be arranged either continually or separately. Wherein, to the continual arrangement is as shown in Fig. 8, wherein the samples 81, 82, 83, 84 formed on the substrate 80 are connected together. The separated arrangement is as shown in Fig. 9, wherein the samples 91, 92, 93, 94 formed on the substrate 90 are arranged in intervals with each other. In other embodiments, the above-mentioned two arrangement manners can be combined. Further, take the oxygen permeable membrane samples as an example, the non-membrane sample regions 85, 95 of the substrate shall not permeate the oxygen to prevent the oxygen from permeating the non-membrane region during the characterizing stage, which may affects the characterizing result, thus if the substrate serves as the supporter material of the membrane, which is porous material and oxygen permeable, it is necessary to deposit an additional oxygen barrier layer thereon to prevent the oxygen from permeating therefrom. The deposited oxygen barrier layer can be composed by any non-air-permeated materials known in the art, such as heating resistant material; and the materials for the dense layer are also usable as it can not permeate oxygen under normal temperature although it can permeate oxygen under a certain temperature.

[41] Further, as to the aspect of high throughput deposition technology, taking the sputtering process as an example, the mask plate used during the sputtering process can be provided in three manners: fixed, movable and rotational. Wherein the fixed providing means that the mask plate is unmovable and the predefined material/element deposit on the predefined region of the substrate through the windows of the mask plate. The movable providing means that the mask plate can move with a controllable speed, thus masking or not of the predefined region of the substrate is achieved by its movement, further windows can also be provided on the mask plate. The rotational providing means that the mask plate can rotate along a predefined axis with a controllable angle and frequency, thus achieve the masking or not of the predefined region of the substrate. Additionally, above-mentioned three providing manners can be used in a combination way. The second and the third providing manners of the mask plate will be illustrated hereinafter.

[42] An embodiment of movable providing mask plate is illustrated in Fig. 10. The sputtering apparatus 100 comprising a plurality of targets 101, 102, 103, 104 can in turn deposit different materials on different regions of the substrate 105 to construct different membrane structure, i.e., each target can be selectively deposited on different regions of the substrate. Specifically, the deposition is performed by the movements of a group of mask plates 106, 107, 108, 109. Further, the deposition on different regions of the substrate can be performed in sequence or in parallel with different design principle of the mask plate.

[43] As shown in Fig. 11, in an embodiment of the mask plate being rotational provided, the sputtering apparatus 110 comprising a plurality of targets 112, 113, 114 can deposit different materials on substrate 115 to construct different membrane structure. Each target can selectively deposit on different regions of the substrate. Specifically, the depositing is achieved by the rotation of mask plates 116, 117. When the mask plate 117 is parallel to the surface of the substrate, the material of the target can not deposit on the region below it; when the mask plate rotates 90 from the direction parallel to the surface of the substrate, the material of the target can deposit on the region. All of the mask plates are controlled by computer to achieve the deposition of different targets or same target on plural predetermined regions.

[44] Additionally, there are various methods for producing membrane samples on a substrate to form a membrane in accordance with the present invention using solution raw materials. For example, in an embodiment, the solution raw materials with relative high viscosity are coated on the substrate to form the different structure membrane samples with two or more dense layers, wherein the viscosity of the solution raw materials relates to the substrate used provided that it does not drop from the substrate. In another embodiment, a film that supports the solution raw materials is provided on the predefined region of the substrate in advance, which can be eliminated by any known method in the art such as burn off at high temperature after the membrane is formed from the solution raw material.

[45] Further, taking an oxygen permeable membrane samples as an example, the method of forming the dense layers of it on a substrate (the substrate can serve as supporter or not) can be any methods disclosed above or any other methods known in the art. In specific embodiments, generally the oxygen permeable region of the substrate is formed after the completion of forming the oxygen barrier region. The materials for the oxygen barrier region can be heating resistant materials, such as ZrO₂, YSZ. The oxygen barrier region can be produced by spraying process, such as suspension spraying process, plasma spraying, spin coating process, sol-gel process, etc; also the process of pulsed laser deposition, sputtering process etc. can be used. The pattern of the oxygen barrier region can be prepared in different methods with the aid of the mask plate. In an embodiment of deposition by spraying or sputtering process, the pattern is formed by the mask plate placed between the substrate and the nozzle/target material during the process of spraying. In another embodiment, the oxygen barrier region having a certain thickness is produced by spraying process etc. in advance, and then the patterned' oxygen permeable region is produced by the air sand blower with the assistance of the mask plate. The materials of the oxygen permeable membrane samples can be any materials disclosed above, such as perovskite and related materials. The materials of the oxygen permeable membrane with two or more dense layers can be doped by noble metals with catalyzing property such as Ag etc., wherein the doped material can be distributed either in the bulk phase or in the surface of the membrane. The oxygen permeable membrane sample may also be produced by the process of PVD such as pulsed laser deposition, sputtering etc., or the process using chemical solution such as sol-gel etc.

[46] In another aspect, the present invention provides a high throughput method for characterizing a membrane with two or more samples thereof, comprising the following steps:

[47] 1) placing a membrane to be characterized with two or more samples on an opening of a first container to form an enclosed first chamber, wherein the first side of the membrane faces the first chamber;

[48] 2) filling the first chamber with one or more predetermined gases;

[49] 3) placing a probe over and close to the second side of the membrane to collect at least one gaseous substance above said samples; and

[50] 4) analyzing the collected gaseous substance to determine the property of said samples.

[51] The first step further comprises the step of placing the second side of the membrane on an opening of a second container to form an enclosed second chamber and placing the probe in the second chamber.

[52] In another embodiment, the membrane with two or more samples are placed in a container and divide the container into a first chamber and a second chamber, wherein the first chamber is filled with at least one predetermined gaseous substance, the gaseous substance may reach the second chamber by passing through the membrane or the sample on the membrane, and a probe is placed in the second chamber.

[53] Further, the properties of the membrane sample that can be obtained based on the analysis result comprise:

[54] 1. The reactive property of the membrane sample; the predetermined gaseous substance disposed in the first chamber reacts with the membrane samples (acting as a reactant) when passing through the membrane to produce gaseous reaction products, the gaseous products will pass through the membrane to the second side of the membrane and be collected by the probe once the reaction happens. Thus, the reactive property of the membrane sample can be evaluated by analyzing the gas substance collected by the probe.

[55] 2. The catalyzing property of the membrane sample; the membrane acting as the catalyst medium accelerates the reaction of the gaseous reactants disposed in the second chamber when they passing through the membrane, the gaseous reaction products will pass through the membrane to the second side of the membrane and be collected by the probe. Thus, the catalyzing property of the membrane sample can be evaluated by analyzing the gas substance collected by the probe.

[56] 3. The gas permeability property; only one or more specific gases can pass through the membrane from its first side to its second side under certain conditions, wherein the membrane only servers as a passing channel. Thus, the gas permeability property of the sample of membrane can be evaluated by analyzing the gas substance collected by the probe.

[57] Further, the gas substance above the second side of each sample is transported by the probe to the detecting device in the process of characterization, which may comprise one or more gaseous substances. The sources of the one or more gaseous substances corresponding to the three characterizing property of the sample respectively comprise: the first source, the reaction products of the one or more gaseous substance disposed in the first chamber with the membrane sample, which pass through the membrane sample to the second side of the membrane; the second source, the reaction products of the two or more gaseous substances disposed in the first chamber with the catalysis of the membrane sample, which pass through the membrane to its second side; the third source, one or more gaseous substances in the first chamber, which pass through the membrane to its second side, or the reaction products of them with the gaseous substance disposed on the second side; accelerating the reaction thereof can increase the vacuum of the gas on the second side in order for more gaseous substance on the first side of the membrane passing through the membrane.

[58] Further, the probe used in the third step of the method is provided with a first channel, a second channel and a nozzle. Wherein the first end opening of the second channel connects to the nozzle, and the nozzle surrounds the first end opening of the first channel, while the nozzle and the first end opening of the first channel are above the second side of the membrane sample to be characterized, and another end of the second channel connects to a gas storage apparatus, and the another end of the first channel connects to the detecting device. The first gas stored in the gas storage apparatus is ejected from the nozzle and the second channel during the process of collecting the gaseous substances, thus a sealed room is formed between the nozzle and the second side of the membrane sample to be characterized, wherein the first gas just function to forming the sealed room and does not take part in any reaction by any means except one case. The exceptional case is that for the purpose of rendering more predetermined gas permeating from the first side of the membrane to its second side, the ejected first gaseous substance reacts with the predetermined gases that pass through the membrane in the sealed room to consume it in order to increase the vacuum of the predetermined gases in the sealed room during the characterization process of gas permeation property of the membrane, which is favorable for more predetermined gas permeating from the first side of the membrane to its second side. Thus, to some extent, the first gas is not injected as the reactants or catalyst, on the contrast it was injected as the first gas to form a stable gaseous sealed room instead of reactant. In the specific embodiments, the first gas can be one or more of inert gas or reducing gas, such as N-, He, H-, CO, CH4, C2H2 etc.

[59] The third step may further comprise a step of gas suction; which suctions the gas surrounding the sealed room to enhance the sealing effect of the sealed room.

[60] The third step may further comprise a step of heating, which heat the predefined region of each membrane sample to a predefined temperature. And to the different membrane samples, the predefined temperature can be different. So the "different membrane samples" used in the specification, if no specially point out, it only means numbers of membrane samples, not different in membrane samples themselves, that is to say, sometimes, they can be the membrane samples with the same constituent structure. For example, in an embodiment, two membrane samples with the same constituent structure are characterized by the characterizing method in accordance with the present invention with a different operation references (such as, different predefined heating temperatures) respectively to get the best utilize condition of the membrane sample with this specific constituent structure.

[61] Further, the detecting device can be any analysis apparatus for gaseous substances, such as gas chromatograph (GC), mass spectra (MS) etc.

[62] Further, there are two manners of sampling the samples of the membrane in the third step. One manner is that one probe is used to collect the gaseous substance over each membrane sample one by one; the other manner is that plurality probes are used to collect the gaseous samples over the same number of the membrane samples in parallel. Further, the two or more membrane samples of the membrane to be characterized can be provide continually and/or separately. The different samples connect with each other in continual manner; the different samples are apart from each other in separated manner. In an embodiment of the continual manner, a plurality of the samples dispose on a membrane in a continual manner (please refer to Fig. 8). In an embodiment in separated manner, a plurality of the samples dispose on a membrane in a discontinual manner (please refer to Fig. 9). Further, the membrane samples to be characterized can have a principle on materials selection, such as the content of the one or more elemtens contained in plurality of samples disposed on a membrane is from high to low; in an embodiment, the structures of the dense layers of five membrane samples disposed on a membrane are Lao.₂Sr₀.8Co0_3-z, La₀₃Sr₀₇CoO_3-Z, La_0.4Sr_0.6 CoO_3-2, Lao_.5Sro_.5CoO₃._z, Lao_.6Sr_0.4Co0₃._z respectively.

[63] Further, in the process of characterization, the first side of the membrane toward the first chamber can be any side of the membrane sample; that is to say, for the sample with multi-layers structure, the probe can be faced by the supporting layer or the dense layer thereof.

[64] In another aspect, the present invention provides a high throughput device for characterizing membrane, it comprises a first container with an opening, a probe and a membrane to be characterized, wherein the membrane comprises more than one membrane samples and is placed on the opening of said first container to form a enclosed first chamber, wherein the first chamber stores one or more predetermined gases; and wherein the probe is placed the-side of the membrane opposite to said first chamber and close to said membrane to collect gaseous substance passing from the first chamber through the membrane samples.

[65] Further, it also comprises a second container with opening, wherein the opening of said second container matches the opening of said first container approximately; the second container is set on the side of the membrane opposite to the first chamber and forms an enclosed second chamber with said membrane; and the probe is placed in the second chamber.

[66] Further, in other embodiment, the first container and second container can originate from a same container, wherein the membrane with two or more samples are placed in it and divide the container into a first chamber and a second chamber, wherein the first chamber is filled with at least one predetermined gaseous substance, the gaseous substance may reach the second chamber by passing through the membrane or the sample on the membrane, and the probe is placed in the second chamber.

[67] Further, the high throughput device for characterizing membrane also comprises a gas storage apparatus and a detecting device; and the probe comprises a first channel, a second channel and a nozzle, and the first channel comprises a first end opening surrounded by the nozzle, and the opposite end of the first channel connects to the detecting device; the second channel comprises a first end opening connecting to the nozzle, and the opposite end of the second channel connects to the gas storage apparatus. The probe in usage sate is located above the second side of the membrane to be characterized so that the first end opening of the first channel and the nozzle are toward the membrane. The first gas stored in the gas storage apparatus ejects toward the first side of the membrane sample through the nozzle and the second channel to form a sealed room isolated from the out environment between the nozzle and the second side of the membrane, wherein, as mentioned above, the first gas does not take part in any reaction except for forming a sealed room to some extent, so that the gaseous substance in the sealed room is collected by the first channel and is transferred to the detecting device for analysis, such as detecting the substances contained therein.

[68] The probe can comprise more than one first channels, but all of the first end openings of the first channels are surrounded by the nozzle, that is to say, the nozzle surround all of the first openings of the first channels used for sampling. The first channel can be provided in the nozzle by any manner. For example, in an embodiment, the first channel is in the center of the region surrounded by the nozzle. In an embodiment of more than one first channels, the more than one first openings are provided in the region surrounded by the nozzle symmetrically.

[69] Further, the probe can comprise two or more second channels, correspondingly, there can be two or more nozzles. In an embodiment, the probe comprises one nozzle and more than one second channel, wherein each first end opening of the second channel connects to the nozzle. In another embodiment, the probe comprises several nozzles and the equal number of the second channels (two or more); each nozzle connects to the responding first end opening of the second channel. In another embodiment, the probe comprises several second channels and less number of nozzles, and each nozzle connects to one or more first openings of the second channels; and there is no limitation on that whether each nozzle connects to the same number of first openings of the second channels. Further, there is no limitation on the providing manner of the second channels, such as being provided symmetrically. And there is no limitation on the shape of the nozzle; for example it can be arc-shaped hole, quadrate-shaped hole, circle-shaped hole, etc.

[70] The probe further comprises at least one third channel, wherein the first end opening locate around the nozzle, and its opposite end opening connects to a suction apparatus to serve as the channel for venting the gas suctioned by the suction apparatus from outside the nozzle. And the outside of the nozzle can also mean the outside of the sealed room formed by the first gaseous substance, thus the sealing effect of the sealed room can be promoted. Further, in an embodiment, the probe comprises one third channel with its first opening as a suction nozzle surrounding the nozzle. In another embodiment, the probe comprises several third channels with their first end openings as a suction nozzle and symmetrically provided around the nozzle. And there is no limitation on the shape of the first end opening of the third channel acting as the pump nozzle; it can be any shape such as arc-shaped hole, quadrate-shaped hole, circle-shaped hole, etc.

[71] Further, the first channel, the second channel and the third channel can be in any shape such as arc-shaped tube, quadrate-shaped tube, circle-shaped tube, etc. without any limitation. For example, the first channel can be capillary channel.

[72] Further, in an embodiment of the probe of the high throughput device for characterizing membrane in accordance with the present invention, with refer to Fig. 12, the probe comprises a body 120 with a first channel 121 defined therein. Several second channels 123 disposed around the first channel symmetrically, and all first end openings of the second channels connect with a first circle shaped close slot 122 serving as a nozzle. Several third channels 125 disposed around the second channels, and their first end openings connect to the second circle shaped close slot 124 serving as sanction nozzle. The second close slot surrounds the first close slot. The first channel, the second channels and the third channels are circle tube shaped channel, and the axes of the second channels 123 and third channels 125 are parallel with the first axis and distributed symmetrically around the first center axis, wherein the center axis of the first channel 121 are taken as the first center axis.

[73] In other embodiments, the longitudinal section of the first and second close slot 122, 124 can be any desired shape, such as oval shape, rectangle shape, triangle shape, and other regular geometry shape or unregulated geometry shape. The blowing property (such as, the pressure and the direction of the blowing) of the first close slot

122 and the sanction property (such as, the pressure and the direction of the sanction) of the second close slot 124 can be changed by changing the longitudinal section of the first close slot and the second close slot 122, 124. [74] Further, in another embodiment of the probe of the high throughput device for characterizing membrane in accordance with the present invention, with refer to Figs.13, 14, the probe is made by assembling, comprising the first component 130 and the second component 132, wherein the first component 130 is provided with a assembling cavity 133, the third channels 135 and the second close slot 137 as the sanction nozzle along the first axis. The second component 132 matches the assembling chamber 133. One or more grooves 136 are provided in the assembling surface that matches with the assembling cavity 133. The grooves 136 extend from one end of the second component 132 to another end. One or more second channels are formed between the assembling chamber 133 and the grooves 136 when the second component 132 is mounted in the assembling cavity 133. A first channel 134 provided in the second component 132 extends from one end of the second component 132 to another end. A ladder portion 138 is provided at the first end of the second component 132, which forms the first close slot with assembling cavity 133 to serve as a nozzle. The direction of the blowing and sanction of the nozzle can be changed by changing the shape of the inter shape (such as, spiral shape) of the second channel and the third channel.

[75] Compared to the prior art, the membrane and the characterizing method thereof in accordance with the present invention provide a new direction to the research on the membrane, and will accelerate the research on the membrane with novel structure and its industrialization.

BRIEF DESCRIPTION OF THE DRAWINGS

[76] Fig. 1 is a scheme of an embodiment of the structure of the supporting layers of the membrane of the present invention;

[77] Fig. 2 is a scheme of an embodiment of the top layer of the supporting layers of the membrane of the present invention;

[78] Fig. 3 is a scheme of another embodiment of the top layer of the supporting , layers of the membrane of the present invention;

[79] Fig. 4 is a scheme of an embodiment of a membrane of the present invention;

[80] Fig. 5 is a chart flow of forming a membrane of the present invention;

[81] Fig. 6 is a chart flow of an another embodiment forming a membrane of the present invention; [82] Fig. 7 is a chart flow of an another embodiment forming a membrane of the present invention;

[83] Fig. 8 is a scheme illustrating a embodiment of the arrangement of the samples disposed on a membrane of the present invention;

[84] Fig. 9 is a scheme illustrating another embodiment of the arrangement of the samples disposed on a membrane of the present invention;

[85] Fig. 10 is a scheme illustrating an embodiment of preparing a membrane of the present invention by sputtering deposition technique, wherein the arrangement of the mask plates is movable;

[86] Fig. 11 is a scheme illustrating another embodiment of preparing a membrane of the present invention by sputtering deposition technique, wherein the arrangement of the mask plates is rotational;

[87] Fig. 12 is a scheme of an embodiment of the probe of the sampling system of the present invention;

[88] Fig. 13 is a scheme of another embodiment of the probe of the high throughput device for characterizing membrane of the present invention, wherein only the first component is shown;

[89] Fig. 14 is a scheme of another embodiment of the probe as shown in Fig. 13, wherein only the second component is shown;

[90] Fig. 15 is a scheme illustrating an embodiment of performing the characterization of the oxygen permeability of the samples of the membrane by using the method of characterizing the membrane of the present invention;

[91] Fig. 16 is a magnified cross-sectional view of a partial view of the Fig. 15.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[92] The following is an embodiment of preparation of a membrane with two or more samples thereof on a substrate of the present invention by the method of the present invention, wherein each sample comprise a single supporting layer and two dense layers.

[93] The process is that: firstly,a Al₂O₃ ceramic plate as substrate and supporting layer is placed into a high throughput sputtering system, then La, Sr, Co, Fe as target materials is sputtered toward the Al₂O₃ ceramic plate. The quantity of each metal deposited on the different regions of the Al₂O₃ ceramic plate is controlled by the movement of the targets and the mask plate during the process of sputtering. The dense layer structures of the membrane samples formed are La_O-2Sr_0-8COo_-2Fe_O-SO_3-2+ Lao.₄Sro.₆Cθo.₂Fe₀.₈θ_3-Zϊ Lao^Sro^Coo^FeagOs^Lao^Sro^Coo^FeasOs^ Lao.₂Sr₀.8Co₀.₄ Fe₀.₆O_3-2 + La_α4 Sr_0-6 Co₀.4 Fe_0-6O_3-^ La_o.₆ Sr_0-4 Co₀.₄ Fe_0-6 O₃._z + La_0-8 Sr_0-2 Co_0-4 Fe_0-6 O₃._z respectively. And the regions of substrate without dense layer thereon is deposited with a layer of La_0-4Sr_0-6Co_{0 8}Fe_0-2O_3-2.

[94] Referring to Figs. 15, 16, an embodiment of characterizing the oxygen permeability of the several samples of the membrane by a high throughput device for characterizing the membrane of the present invention is shown. The operation of the device follows the steps of the high throughput method for characterizing membrane of the present invention.

[95] Firstly, a membrane 151 with several samples 152 provided in an apart manner thereof is placed into the first sealed room 150, wherein the first sealed room is divided into two unconnected the first chamber and the second chamber by the membrane 151 itself as boundary. The first side of the membrane 151 faces the first chamber, and the opposite second side of the membrane faces the second chamber.

And the second chamber is filled with a mixture gas containing a certain proportion of 02.

[96] Secondly, the first end of the probe 160 of the high throughput device for characterizing membrane of the present invention is placed into the first chamber with its first end opening of the first channel 162 and the nozzle 164 being above the membrane to be characterized, wherein the opposite end of the first channel connects with a mass spectral apparatus 153, and the nozzle 164 connects with a gas storage apparatus 154 storing H2 therein through the second channel 163, and the sanction nozzle 166 connects a air pump 155 through the third channel 165. In the process of characterization, the predetermined region of the first sample to be characterized is heated by a laser 156 with a 10 um wavelength to 850 ^"C to activate its oxygen permeability; and the H2 ejected from the nozzle forms the second sealed room between the nozzle and the first side of the corresponding first sample to be characterized. The H2 reacts with the 02 permeated through the membrane to increase the O2 vacuum of the second sealed room so that it is preferable for more 02 permeating through the membrane. The pump sanctions the gas around the nozzle 164 through the third channel 165 and sanction nozzle 166 to enhance the isolation effect of the second sealed room. The mass spectral apparatus analyzes the gas sample collected by the first channel to obtain the data of the oxygen content, and then obtain the oxygen permeability of the first sample to be characterized. Additionally, a mixture gas with a certain proportion of 02 can be blown toward the second side of the membrane to be characterized through another tube (not shown) to increase the 02 permeating rate.

[97] Thirdly, repeat the first and the second step to complete the characterization of the oxygen permeability of each sample of the membrane to be characterized.

Claims

1. A high throughput method for characterizing membrane, comprising the steps of:

1) placing a membrane to be characterized with two or more samples on an opening of a first container to form an enclosed first chamber, wherein the first side of the membrane faces the first chamber;

2) filling the first chamber with one or more predetermined gases;

3) placing a probe over and close to the second side of the membrane to collect at least one gaseous substance above said samples; and

4) analyzing the collected gaseous substance to determine the property of said samples.

2. The high throughput method for characterizing membrane according to claim 1, further comprises the steps of placing the second side of the membrane on an opening of a second container to form a enclosed second chamber and placing the probe in the second chamber.

3. The high throughput method for characterizing membrane according to claim 2, wherein the first chamber and the second chamber can be formed by placing the membrane into a storage room and having the membrane divide the room into the first and second chambers; wherein the predetermined gases in the first chamber can reach the second chamber by passing through the membrane.

4. The high throughput method for characterizing membrane according to claim 1, wherein the obtainable properties of each sample of the membrane to be characterized comprise one or more of the followings: the reacting property, catalyzing property and the gas permeability property.

5. The high throughput method for characterizing membrane according to claim

1, wherein the sources of the one or more gaseous substances collected by the probe can be 1) : a first source wherein the predetermined gases react with said sample on the membrane and pass through the membrane to the second side; 2) a second source wherein the predetermined gases react with each other in the presence of said sample as being a catalyst and pass through the membrane to the second side, and 3) a third source wherein the predetermined gases pass through the sample.

6. The high throughput method for characterizing membrane according to claim I₅ wherein the probe collects the gaseous substance sequentially from each said sample.

7. The high throughput method for characterizing membrane according to claim I₅ wherein the probe collects the gaseous substance in each said sample in parallel.

8. The high throughput method for characterizing membrane according to claim I₅ wherein the samples of the membrane to be characterized are continually provided thereon.

9. The high throughput method for characterizing membrane according to claim 1, wherein the samples of the membrane to be characterized are separately provided thereon.

10. The high throughput method for characterizing membrane according to claim I₅ wherein the samples to be characterized comprise oxygen permeable membrane sample/samples.

11. The high throughput method for characterizing membrane according to claim 1, wherein the probe used in the second step is provided with a first channel, a second channel and a nozzle, wherein the first end opening of the second channel connects with the nozzle; and the nozzle surrounds the first end opening of the first channel; and the nozzle and the first end opening of the first channel are above the first side of the sample to be characterized; and another end of the second channel connects with a gas storage apparatus storing the first gas; and the another end of the first channel connects with the detecting device; the first gas stored in the gas storage apparatus is ejected through the second channel and the nozzle during the process of sampling, thus a sealed room is formed between the nozzle and the second side of the membrane sample to be characterized; and wherein the first gas just function to forming a stable gas sealed room to some extent instead of being injected as a reactant or catalyst.

12. The high throughput method for characterizing membrane according to claim 11, wherein the third step further comprises a gas sanction step, which sanctions the gas/gases around the sealed room formed by the first gas to enhance the sealing effect of the sealed room.

13. The high throughput method for characterizing membrane according to claim 1, wherein the third step further comprises a heating step, which heats the predetermined region/regions of each membrane to a predetermined temperature.

14. The high throughput method for characterizing membrane according to claim I₅ wherein each sample comprises one or more supporting layers and one or more dense layers provided thereon.

15. The membrane according to claim 14, wherein the sample comprises at least two dense layers.

16. The membrane according to claim 14, wherein the sample comprises at least two supporting layers, and the pore size of the material of the bottom layer is in the range of 100 nm to 100 μm, and the pore size of the material of the top layer of the supporter is in the range of 1 nm to 100 nm.

17. The membrane according to claim 16, wherein the sample comprises at least three supporting layers.

18. The membrane according to claim 14, wherein the pore size of each material contained in the sample reduced in gradient from the bottom layer to the top layer.

19. The membrane according to claim 14, wherein the samples are oxygen permeable membrane samples.

20. A high throughput device for characterizing membrane, comprising a first container with a first opening, a probe and a membrane to be characterized, wherein the membrane comprises more than one membrane samples and is placed on the first opening of said first container to form an enclosed first chamber, wherein the first chamber stores one or more predetermined gases; and wherein the probe is placed the side of the membrane opposite to said first chamber and close to said membrane to collect at least one gaseous substance passing from the first chamber through the membrane samples.

21. The high throughput device for characterizing membrane according to claim 20, it further comprises a second container with a second opening, wherein the second container is set on the side of the membrane opposite to the first chamber and forms an enclosed second chamber with said membrane; and the probe is placed in the second chamber.

22 The high throughput device for characterizing membrane according to claim 21, wherein the second opening of said second container matches the first opening of said first container approximately

23 The high throughput device for characterizing membrane according to claim 21, wherein the first container and second container can originate from a same container, and the membrane is placed in and divides the same container into the first chamber and the second chamber.

24. The high throughput device for characterizing membrane according to claim 20, further comprising a gas storage apparatus and a detecting device; and the probe comprises a first channel, a second channel and a nozzle, and the first end opening of the first channel is surrounded by the nozzle, and the other end of the first channel connects with the detecting device; the first end opening of the second channel connects with the nozzle, and the other end of the second channel connects with the gas storage apparatus.

25. The high throughput device for characterizing membrane according to claim 24, which further comprises a gas sanction apparatus, and the probe further comprises a third channel, and the first end opening of the third channel is located around the nozzle, and the other end of the third channel connects to the gas sanction apparatus.