CN101311720A - Knudsen Cell-mass spectrometer for gas adsorbing /desorption kinetic determination - Google Patents
Knudsen Cell-mass spectrometer for gas adsorbing /desorption kinetic determination Download PDFInfo
- Publication number
- CN101311720A CN101311720A CNA2007100994426A CN200710099442A CN101311720A CN 101311720 A CN101311720 A CN 101311720A CN A2007100994426 A CNA2007100994426 A CN A2007100994426A CN 200710099442 A CN200710099442 A CN 200710099442A CN 101311720 A CN101311720 A CN 101311720A
- Authority
- CN
- China
- Prior art keywords
- mass spectrometer
- knudsen cell
- sample
- cell
- knudsen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000003795 desorption Methods 0.000 title abstract description 13
- 230000007704 transition Effects 0.000 claims abstract description 14
- 238000009529 body temperature measurement Methods 0.000 claims abstract description 5
- 238000009530 blood pressure measurement Methods 0.000 claims abstract description 4
- 238000005259 measurement Methods 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 239000000843 powder Substances 0.000 abstract description 13
- 230000001052 transient effect Effects 0.000 abstract description 7
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
本发明属于质谱仪器技术领域。具体而言，本发明提供了一种努森池－质谱仪。其可用于瞬态气体吸附/脱附动力学、吸附量/脱附量的测定。其包括气体泄漏阀、努森池、连续可调虹膜或可更换泄漏孔、过渡室、门阀、质谱仪、温度测量系统、温度控制系统、压力测量系统和压力控制系统。气体泄漏阀作为常压和低压的接口，可控制进入真空系统的气体量。努森池由可垂直运动的样品盖、固定的样品池、温度和压力测量控制系统构成。质谱仪作为气体检测器。所有腔体内表面经表面处理，具有化学惰性。本发明提供的努森池质谱仪可精确测定气体在粉末样品上的吸附脱附动力学常数和吸附量，尤其适用于物理化学领域、大气环境领域的相关研究。
The invention belongs to the technical field of mass spectrometers. Specifically, the invention provides a Knudsen cell-mass spectrometer. It can be used for the determination of transient gas adsorption/desorption kinetics, adsorption capacity/desorption capacity. These include gas leak valves, Knudsen cells, continuously adjustable iris or replaceable leak holes, transition chambers, gate valves, mass spectrometers, temperature measurement systems, temperature control systems, pressure measurement systems, and pressure control systems. The gas leak valve is used as an interface for normal pressure and low pressure to control the amount of gas entering the vacuum system. The Knudsen cell consists of a vertically movable sample cover, a fixed sample cell, and a temperature and pressure measurement control system. A mass spectrometer acts as a gas detector. All chamber interior surfaces are surface treated to be chemically inert. The Knudsen cell mass spectrometer provided by the invention can accurately measure the adsorption-desorption kinetic constant and adsorption amount of gas on powder samples, and is especially suitable for related research in the fields of physical chemistry and atmospheric environment.
Description
技术领域 technical field
本发明属于质谱仪器技术领域。具体涉及努森池和质谱仪。The invention belongs to the technical field of mass spectrometers. Specifically related to Knudsen cells and mass spectrometers.
背景技术 Background technique
气体在固体粉末样品上的摄取(吸附、吸收、催化反应)和脱附是大气环境化学和物理化学领域的重要过程。在大气环境领域，痕量气体在固体粉末样品上的摄取系数是研究痕量气体在环境微界面上迁移转化规律的不可缺少的动力学参数。在物理化学领域，气体在固体粉术样品上的瞬态吸附/脱附速率常数、吸附量/脱附量也是研究气-固界面的微观过程的重要参数。The uptake (adsorption, absorption, catalytic reaction) and desorption of gases on solid powder samples is an important process in the field of atmospheric environmental chemistry and physical chemistry. In the field of atmospheric environment, the uptake coefficient of trace gas on solid powder samples is an indispensable kinetic parameter to study the migration and transformation of trace gas on the micro-interface of the environment. In the field of physical chemistry, the transient adsorption/desorption rate constant, adsorption amount/desorption amount of gas on solid powder samples are also important parameters for studying the microscopic process of gas-solid interface.
目前，基于布朗诺尔-埃米特-泰勒(BET)多层吸附理论的比表面积测定仪，可用于气体在固体粉末样品表面的吸附量的测定。例如Quantachrome Instruments、Micromeritics公司等生产的比表面积测定仪均可用于气体在固体粉末样品上物理、化学吸附量测定。然而，该方法属于稳态测定方法、耗时长，而且不能测定瞬态吸附速率常数。程序升温脱附(TPD)常用于固体粉末样品上气体脱附过程的测定。其中利用质谱为检测器的TPD-MS可以测定气体的瞬态脱附过程，但是不能同时获得吸附过程的信息。而利用努森池和质谱仪连接，努森池中粉末样品可暴露或隔离于被测气体气氛，从而可以在完成气体在粉末样品上的吸附速率常数和吸附量测定后，进一步测定其脱附速率常数和脱附量；利用质谱仪的高时间分辨率，可以获得瞬态动力学数据，从而为快速测定气体在粉末样品上吸附/脱附动力学、吸附量/脱附量提供了新的思路。At present, the specific surface area measuring instrument based on Brownauer-Emmett-Taylor (BET) multilayer adsorption theory can be used for the determination of the adsorption amount of gas on the surface of solid powder samples. For example, the specific surface area measuring instruments produced by Quantachrome Instruments and Micromeritics can be used to measure the physical and chemical adsorption of gases on solid powder samples. However, this method belongs to the steady-state determination method, takes a long time, and cannot determine the transient adsorption rate constant. Temperature-programmed desorption (TPD) is commonly used for the determination of gas desorption processes on solid powder samples. Among them, TPD-MS using mass spectrometry as the detector can measure the transient desorption process of gas, but cannot obtain the information of the adsorption process at the same time. With the connection between the Knudsen cell and the mass spectrometer, the powder sample in the Knudsen cell can be exposed or isolated from the gas atmosphere to be measured, so that after the determination of the adsorption rate constant and adsorption amount of the gas on the powder sample, the desorption can be further measured. Rate constant and desorption amount; using the high time resolution of the mass spectrometer, transient kinetic data can be obtained, thus providing a new method for the rapid determination of gas adsorption/desorption kinetics, adsorption amount/desorption amount on powder samples train of thought.
发明内容 Contents of the invention
本发明结合了努森池和质谱仪的优点，提供的努森池-质谱仪，可在-60℃-250℃范围内快速测定气体在固体粉末样品上的瞬态吸附/脱附动力学、吸附量/脱附量。The present invention combines the advantages of the Knudsen cell and the mass spectrometer, and provides the Knudsen cell-mass spectrometer, which can quickly measure the transient adsorption/desorption kinetics, Adsorption capacity/desorption capacity.
本发明提供的努森池-质谱仪如图1所示，包括气体泄漏阀(1)、努森池(2)、连续可调虹膜(3)、过渡室(4)、门阀(5)、小孔、质谱真空腔(6)、温度控制系统(14)、温度测量系统(15)、压力测量系统(8)和压力控制系统(9)，其中泄漏阀、努森池、连续可调虹膜或可更换泄漏孔、过渡室、门阀、质谱仪依次连接。The Knudsen cell-mass spectrometer provided by the present invention is shown in Figure 1, comprises gas leakage valve (1), Knudsen cell (2), continuously adjustable iris (3), transition chamber (4), gate valve (5), Aperture, mass spectrometer vacuum chamber (6), temperature control system (14), temperature measurement system (15), pressure measurement system (8) and pressure control system (9), among which leakage valve, Knudsen cell, continuously adjustable iris Or replaceable leakage hole, transition chamber, gate valve, mass spectrometer connected in sequence.
本发明的努森池包括独立的真空腔、气体进样接口、气体逃逸孔接口、真空规接口、样品池、样品盖、样品台、循环流体温度控制和测量系统。努森池所有内表面镀特氟龙膜进行表面惰化处理，以消除器壁对气体组分的吸附。样品池置于内埋铂电阻温度计的样品台上，其测量范围为-100℃-250℃，测量误差为±0.1℃。样品台和样品盖之间用特氟龙O型圈密封。样品盖与可垂直移动的拉伸杆相连，从而可将样品隔离或暴露于气体组分中。本发明的样品温度由循环流体介质控制。可从-60℃～0℃和0℃～250℃分段连续可调，其误差范围为±0.1℃。The Knudsen cell of the present invention includes an independent vacuum chamber, a gas sampling interface, a gas escape hole interface, a vacuum gauge interface, a sample pool, a sample cover, a sample stage, a circulating fluid temperature control and measurement system. All inner surfaces of the Knudsen pool are coated with Teflon film for surface inert treatment to eliminate the adsorption of gas components on the wall. The sample cell is placed on the sample stage with a built-in platinum resistance thermometer, the measurement range is -100°C-250°C, and the measurement error is ±0.1°C. Teflon O-rings are used to seal between the sample stage and the sample cover. The sample cover is attached to a vertically movable stretch rod to isolate or expose the sample to gaseous components. The sample temperature of the present invention is controlled by a circulating fluid medium. It can be continuously adjusted in sections from -60°C to 0°C and 0°C to 250°C, and the error range is ±0.1°C.
本发明的过渡室与差分泵(涡轮分子泵)及前级泵连接。质谱真空腔与涡轮分子泵及前级泵连接。努森池和过渡室用连续可调虹膜或可更换泄漏孔连接，从而控制努森池的工作压力。过渡室和质谱真空腔的压力由独立的真空规分别测定。过渡室和质谱真空腔之间用门阀连接。门阀用于更换样品时，确保质谱系统的真空度不变。质谱仪检测器前置一个小孔用于限制进入质谱检测器的气体流量。The transition chamber of the present invention is connected with a differential pump (turbomolecular pump) and a backing pump. The mass spectrometer vacuum chamber is connected with the turbomolecular pump and the backing pump. The Knudsen cell and transition chamber are connected with a continuously adjustable iris or replaceable leak orifice to control the working pressure of the Knudsen cell. The pressures of the transition chamber and the mass spectrometer vacuum chamber are respectively measured by independent vacuum gauges. A gate valve is used to connect the transition chamber and the mass spectrometer vacuum chamber. The gate valve is used to ensure constant vacuum of the mass spectrometry system when changing samples. A small hole in front of the mass spectrometer detector is used to limit the gas flow into the mass spectrometer detector.
本发明的质谱仪用于气体组分浓度的在线检测。The mass spectrometer of the invention is used for online detection of gas component concentration.
附图说明 Description of drawings
图1为努森池-质谱仪的结构总图。Figure 1 is a general diagram of the structure of the Knudsen cell-mass spectrometer.
图1中标号：1为泄漏阀，2为努森池，3为连续可调虹膜，4为过渡室，5为门阀，6为质谱真空腔，7为质谱RF头，8为真空规，9为涡轮分子泵。Numbers in Figure 1: 1 is the leak valve, 2 is the Knudsen cell, 3 is the continuously adjustable iris, 4 is the transition chamber, 5 is the gate valve, 6 is the mass spectrometer vacuum chamber, 7 is the mass spectrometer RF head, 8 is the vacuum gauge, 9 for turbomolecular pumps.
图2为努森池的结构示意图。Figure 2 is a schematic diagram of the structure of the Knudsen cell.
图2中标号：10为接虹膜法兰，11为样品盖拉伸杆，12为接真空规法兰，13为接泄漏阀法兰，14为循环加热(冷却)介质导管，15为热电偶，16为努森池腔体，17样品盖，18样品台。Numbers in Figure 2: 10 is the iris flange, 11 is the sample cover tensile rod, 12 is the vacuum gauge flange, 13 is the leakage valve flange, 14 is the circulating heating (cooling) medium conduit, 15 is the thermocouple , 16 is the chamber of the Knudsen cell, 17 is the sample cover, and 18 is the sample stage.
图3为羰基硫(OCS)气体在α-Fe2O3上的吸附动力学曲线。Fig. 3 is the adsorption kinetic curve of carbonyl sulfide (OCS) gas on α-Fe 2 O 3 .
具体实施方式 Detailed ways
下面结合附图和实施例对本发明作进一步描述：The present invention will be further described below in conjunction with accompanying drawing and embodiment:
本实施例中，努森池如图2所示。努森池腔体采用精加工的不锈钢圆筒为材料，外径为60mm，内径为56mm，高度60mm。样品台为外径46mm，高度10mm的不锈钢圆片，其正面有一个直径30mm，深度1.5mm的槽口和外径40mm，内径33mm，深度2.2mm的O型圈槽口。样品台中内埋-100℃～250℃的铂电阻温度计。样品台置于外径46mm，高度23mm的圆通上，其与努森池底座共同构成一个腔体，用于循环流动介质对样品进行温度控制。样品池为内径26mm，深度1mm的不锈钢浅槽。样品盖为直径46mm，厚度3mm的盲法兰。其与可垂直运动的拉伸杆连接。拉伸杆和努森池盖之间用O型圈密封。努森池腔体上分别接2个CF16的法兰和1个CF63法兰，分别与泄漏阀、真空规、虹膜或可更换泄漏孔连接。努森池所有内表面都镀特富龙膜。In this embodiment, the Knudsen pool is shown in FIG. 2 . The chamber of the Knudsen pool is made of a precision-machined stainless steel cylinder, with an outer diameter of 60mm, an inner diameter of 56mm, and a height of 60mm. The sample stage is a stainless steel disc with an outer diameter of 46mm and a height of 10mm. On the front, there is a notch with a diameter of 30mm and a depth of 1.5mm and an O-ring notch with an outer diameter of 40mm, an inner diameter of 33mm and a depth of 2.2mm. A platinum resistance thermometer of -100°C to 250°C is embedded in the sample stage. The sample stage is placed on a circular tube with an outer diameter of 46 mm and a height of 23 mm, which together with the base of the Knudsen cell form a cavity for circulating the flow medium to control the temperature of the sample. The sample cell is a stainless steel shallow groove with an inner diameter of 26mm and a depth of 1mm. The sample cover is a blind flange with a diameter of 46 mm and a thickness of 3 mm. It is connected to a vertically movable stretch rod. An O-ring seal is used between the stretch rod and the Knudsen cell cover. Two CF16 flanges and one CF63 flange are respectively connected to the chamber of the Knudsen cell, which are respectively connected with leak valves, vacuum gauges, iris or replaceable leak holes. All interior surfaces of the Knudsen pool are coated with Teflon.
本实施例中，将粉末样品置与样品池中，关闭样品盖，调节泄漏阀和虹膜至努森池中到达适当的压力或气体分子浓度。当质谱信号达稳态后，打开样品盖，获得气体在粉末样品上的吸附动力学数据。通过气体分子流量校正，可获得气体在粉末样品上的吸附量。吸附饱和后，依次关闭样品盖、泄漏阀，完全打开虹膜。至整个体系真空度稳定后，打开样品盖，获得脱附动力学数据和脱附量。In this embodiment, the powder sample is placed in the sample cell, the sample cover is closed, and the leak valve and iris are adjusted to the Knudsen cell to reach an appropriate pressure or concentration of gas molecules. When the mass spectrum signal reached a steady state, the sample cover was opened to obtain the adsorption kinetic data of the gas on the powder sample. By correcting the flow rate of gas molecules, the adsorption amount of gas on the powder sample can be obtained. After the adsorption is saturated, close the sample cover, leak valve in turn, and fully open the iris. After the vacuum degree of the whole system is stable, the sample cover is opened to obtain the desorption kinetic data and desorption amount.
本实施例中，图3为羰基硫(OCS)气体在141.3mgα-Fe2O3上的吸附动力学曲线。根据努森池基本方程，可以计算瞬态吸附/脱附动力学常数。并根据气态分子消耗数量可以测定饱和吸附量。In this embodiment, Fig. 3 is the adsorption kinetic curve of carbonyl sulfide (OCS) gas on 141.3 mg α-Fe 2 O 3 . According to the Knudsen cell fundamental equation, the transient adsorption/desorption kinetic constants can be calculated. And according to the consumption quantity of gaseous molecules, the saturated adsorption capacity can be determined.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100994426A CN101311720A (en) | 2007-05-21 | 2007-05-21 | Knudsen Cell-mass spectrometer for gas adsorbing /desorption kinetic determination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100994426A CN101311720A (en) | 2007-05-21 | 2007-05-21 | Knudsen Cell-mass spectrometer for gas adsorbing /desorption kinetic determination |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101311720A true CN101311720A (en) | 2008-11-26 |
Family
ID=40100446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100994426A Pending CN101311720A (en) | 2007-05-21 | 2007-05-21 | Knudsen Cell-mass spectrometer for gas adsorbing /desorption kinetic determination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101311720A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103592360A (en) * | 2013-10-21 | 2014-02-19 | 清华大学 | High-atmospheric-pressure differential extraction particle beam mass spectrum measurement system |
| CN104576289A (en) * | 2014-12-31 | 2015-04-29 | 聚光科技(杭州)股份有限公司 | Inductively coupled plasma mass spectrometer capable of regulating vacuum pressure |
| CN109742010A (en) * | 2018-11-23 | 2019-05-10 | 暨南大学 | Vacuum sample change method for vacuum instruments |
| CN111201437A (en) * | 2017-10-13 | 2020-05-26 | 身体感官公司 | Fluid sensing device for portable electronic device |
| CN113970591A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院大连化学物理研究所 | A TPD system and method of use based on ultra-high vacuum equipment |
-
2007
- 2007-05-21 CN CNA2007100994426A patent/CN101311720A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103592360A (en) * | 2013-10-21 | 2014-02-19 | 清华大学 | High-atmospheric-pressure differential extraction particle beam mass spectrum measurement system |
| CN103592360B (en) * | 2013-10-21 | 2016-09-21 | 清华大学 | Hyperbar differential extraction particle beam mass-spectrometer measurement system |
| CN104576289A (en) * | 2014-12-31 | 2015-04-29 | 聚光科技(杭州)股份有限公司 | Inductively coupled plasma mass spectrometer capable of regulating vacuum pressure |
| CN104576289B (en) * | 2014-12-31 | 2017-08-25 | 聚光科技(杭州)股份有限公司 | A kind of icp mses of adjustable vacuum pressure |
| CN111201437A (en) * | 2017-10-13 | 2020-05-26 | 身体感官公司 | Fluid sensing device for portable electronic device |
| CN109742010A (en) * | 2018-11-23 | 2019-05-10 | 暨南大学 | Vacuum sample change method for vacuum instruments |
| CN109742010B (en) * | 2018-11-23 | 2021-03-23 | 暨南大学 | Vacuum sample feeding and changing method for vacuum instrument |
| CN113970591A (en) * | 2020-07-22 | 2022-01-25 | 中国科学院大连化学物理研究所 | A TPD system and method of use based on ultra-high vacuum equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8424367B2 (en) | Systems and methods for measurement of gas permeation through polymer films | |
| JP4787344B2 (en) | Humidity control system for detection cell of specimen transmission inspection device | |
| CN103592206B (en) | A kind of hydrogen in metal diffusion or permeance property method of testing and special purpose device thereof | |
| CN103278531B (en) | Device and method for synchronously tracking and measuring microcalorie change in gas-solid adsorption process | |
| CN101311720A (en) | Knudsen Cell-mass spectrometer for gas adsorbing /desorption kinetic determination | |
| CA2947079A1 (en) | Apparatus for volatile organic compound (voc) detection | |
| Fan et al. | SOFC detector for portable gas chromatography: High-sensitivity detection of dissolved gases in transformer oil | |
| CN106525683B (en) | A kind of film permeation rate measuring device and measurement method | |
| US7850918B2 (en) | Multiple sample gas sorption tester | |
| CN110308216A (en) | The integrated analysis system and its application method of micro permanent foreign gas and water in a kind of gas | |
| CN105352855A (en) | System and method for measuring gas diffusion performance of coating | |
| US7398681B2 (en) | Gas sensor based on dynamic thermal conductivity and molecular velocity | |
| Jung | Review of developed methods for measuring gas uptake and diffusivity in polymers enriched by pure gas under high pressure | |
| Lomax | Permeation of gases and vapours through polymer films and thin sheet—part I | |
| Tweedie et al. | The analysis of dissolved inorganic carbon in liquid using a microfluidic conductivity sensor with membrane separation of CO 2 | |
| CN103674800B (en) | A kind of measurement mechanism of hyposmosis rock sample permeability and measuring method thereof | |
| CN114624319B (en) | Method for quantitatively obtaining ppm-level hydrogen isotope content in material based on thermal analysis-quadrupole mass spectrometry measurement principle | |
| RU2341790C1 (en) | Method of gas sensor calibration | |
| CN113866095A (en) | In-situ spectral analysis pool for gas-sensitive sensing exploration and application | |
| WO2013189175A1 (en) | Method and device for measuring concentration of substance in fluid | |
| Lazik et al. | A new method for membrane-based gas measurements | |
| CN106841482B (en) | A kind of application process of gas chromatograph vacuum sampling device | |
| CN113281385A (en) | Portable air blowing type alcohol concentration measuring device and measuring method | |
| CN112834562A (en) | Device and method for detecting helium concentration in thermally conductive mixed gas | |
| CN206920272U (en) | A kind of device for measuring carbon monoxide transmitance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20081126 |