US20030183517A1 - Polymer electrolyte, half cell for electrochemical measurements, and the use thereof - Google Patents
Polymer electrolyte, half cell for electrochemical measurements, and the use thereof Download PDFInfo
- Publication number
- US20030183517A1 US20030183517A1 US10/396,401 US39640103A US2003183517A1 US 20030183517 A1 US20030183517 A1 US 20030183517A1 US 39640103 A US39640103 A US 39640103A US 2003183517 A1 US2003183517 A1 US 2003183517A1
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- US
- United States
- Prior art keywords
- polymer electrolyte
- substituted alkyl
- alkyl group
- methacrylate
- half cell
- 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.)
- Abandoned
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
Abstract
Description
- This application claims priority under 35 U.S.C. §119 to German Patent Application No. 10214035.9 filed in Germany on Mar. 27, 2002, the entire content of which is hereby incorporated by reference.
- 1. Field of the Invention
- The invention relates to a polymer electrolyte, to a half cell, and to uses of the half cell and of the polymer electrolyte.
- 2. Prior Art
- Numerous half cells for electrochemical measurements, such as potentiometric or amperometric measurements, are known. In particular, such half cells can be embodied as reference electrodes, which are used in combination with potentiometric or amperometric sensors. In such reference electrodes, it is imporant that they output as constant a reference potential as possible.
- In one type of reference electrodes, there is a fluid reference electrolyte, such as an aqueous potassium chloride solution, which can be brought into contact with a fluid measuring medium via a liquid connection (also known as a “liquid junction”). To avoid or reduce an unwanted mass transfer between the measuring medium and the reference electrolyte, the liquid junction is typically designed as a more or less porous diaphragm. One disadvantage of such liquid junctions, however, is that soiling or even plugging up of the pores can occur, which can lead to considerable faulty potentials and possibly interruptions.
- In another type of reference electrodes, instead of the diaphragm, a single opening or a plurality of openings is provided, as a result of which the aforementioned problem of soiling can be largely avoided. However, this embodiment means that instead of the otherwise usual fluid or gel-like reference electrolyte, a non-flowable reference electrolyte is used, to prevent the reference electrolyte from flowing out. A polymer electrolyte in the form of a hydrogel, which for instance contains a saturated aqueous potassium chloride solution and preferably additionally suspended potassium chloride is especially well suited for this purpose.
- In European Patent Disclosure EP 1124132 A1, which is hereby incorporated by reference in its entirety, a reference electrode of this generic type is described which contains a polymer electrolyte that contains a polymer on the basis of monomers selected from N-substituted acrylamides and/or methacrylates. For instance, the methacrylate is a methacrylate with at least two hydroxy groups, and in particular 2,3-dihydroxypropyl methacrylate.
- An object of the invention is to furnish further polymer electrolytes which are especially well suited for electrochemical half cells and in particular for reference half cells. Other objects of the invention are to furnish an improved half cell and to disclose uses of the half cell and of the polymer electrolytes.
- The polymer electrolytes of the invention contain a polymer which as a first monomer component contains at least one alkyl methacrylate. The aforementioned alkyl methacrylate has a substituted alkyl group with from three to seven carbon atoms and at least two substituents, and the aforementioned substituents are selected from the group comprising OR1 and NR2R3, and R1, R2 and R3 are selected from the group comprising hydrogen, methyl, and ethyl, on the condition that the substituted alkyl group contains the substituent OH at most once. By a suitable selection of the substituents in the aforementioned range, the properties of the polymer electrolyte, in particular its polarity and hence its resistance and stability to water or to polar or apolar solvents, can be adapted accordingly to the intended area of use. Moreover, the polymer electrolytes of the invention are distinguished by good resistance and stability to acids.
- The half cell of the invention, which can be used as a component in potentiometric or amperometric sensors, contains one of the polymer electrolytes of the invention. The polymer electrolyte of the invention can also be used as a solid-phase electrolyte in a battery half cell.
- Exemplary embodiments are directed to the substituted alkyl group of the alkyl methacrylate intended as the first monomer component. According to exemplary embodiments, the substituted alkyl group is a 3-amino-2-hydroxypropyl or a 2-amino-3-hydroxypropyl. Moreover, in accordance in exemplary embodiments, the substituted alkyl group may be a 3-diethylamino-2-hydroxypropyl, a 3-ethoxy-2-hydroxypropyl, a 3-methoxy-2-hydroxypropyl, or a 3- methylamino-2-hydroxypropyl. Furthermore, according to exemplary embodiments, the substituted alkyl group can be a —CH2—CH2OH—CH2—NR2R3 or a —CH2—CH2—NR2R3—CH2OH, in which R2 and R3, are as described above. Also, the substituted alkyl group can be a —CH2—CH2OH—CH2—OR4 or a —CH2—CH2—OR4—CH2OH, in which R4 is a methyl or ethyl. However, a mixture of alkyl methacrylates of the type named above can also be contemplated as the first monomer component.
- According to exemplary emboidments, the polymer contains, as a further monomer component, a hydroxyalkyl methacrylate, which is preferably 2-hydroxyethyl methacrylate and/or 3-hydroxypropyl methacrylate. With this further monomer component, the polarity of the polymer electrolyte can advantageously be varied, and by a choice of the quantity ratio of the further monomer component to the first monomer component, the polarity is adjustable over a wide range.
- Exemplary embodiments can be used in conjunction with a half cell with a glass housing. Because the polymer contains, as an additional monomer component, a silylated alkyl methacrylate, preferably 3-(trimethoxysilyl)propyl methacrylate, an adhesion of the polymer electrolyte to the glass housing is achieved, as a result of which a longer service life of the half cell and in particular better resistance to pressure and washing out is attained.
- Exemplary embodiments are directed to a polymer electrolyte. This polymer electrolyte can additionally contain a concentrated aqueous solution of a salt or salt mixture, which is indicated for use in polar measuring media. The polymer electrolyte can contain a mixture of an organic solvent and an aqueous solution of a salt and is accordingly predominantly usable for less-polar measuring media. The organic solvent is selected from the group comprising glycerine, ethylene glycol, methanol, ethanol, N-propanol, isopropanol, acetone, and mixtures thereof. It is especially advantageous if the salt is additionally in the form of a suspension. As a result of the increased salt content, a longer resistance of the half cell to washing out of the salt as a result of the contact with the measuring medium is achieved. On the other hand, the progressive depletion of the salt caused by the washing out can be readily ascertained visually from the developing washing-out or depletion front, which forms the boundary between a region of the polymer electrolyte that is clouded by the salt suspension and a region of the polymer electrolyte that is more clear because the salt suspension is no longer present there. For instance, the aforementioned salt is selected from the group comprising potassium chloride, sodium chloride, lithium chloride, potassium nitrate, potassium perchlorate, sodium formiate, lithium acetate, lithium sulfate, ammonium chloride, methylammonium chloride, dimethylammonium chloride, trimethylammonium chloride, and mixtures thereof. This salt can, however, also be a further ionic organic halide, for instance. This salt can also form a redox system.
- The half cell can have an open liquid junction between the polymer electrolyte and a surrounding medium—as a rule, a measuring medium or a fluid specimen. This embodiment is possible because the polymer electrolyte is essentially in solid form and accordingly cannot escape from the open liquid junction. By dispensing with a diaphragm, unwanted interfering potentials in the region of the liquid junction can be largely avoided.
- The sole drawing FIGURE schematically shows a reference electrode for electrochemical measurements in longitudinal section.
- The reference electrode shown in the drawing has a
tubular housing 2, made from glass or plastic, whoselower end 4, in the example shown, is immersed in ameasuring medium 6. The interior of thehousing 2 is filled with apolymer electrolyte 8, in which a lead-offelement 10 is immersed. The lead-off element is formed for instance by a chlorinated silver wire, which is extended to the outside through anupper cap part 12 of thehousing 2. Anopening 14 in the vicinity of thelower end 4 serves as liquid junction between thepolymer electrolyte 8 and the measuringmedium 6. - The
polymer electrolyte 8 is advantageously formed in the interior of thehousing 2; first the requisite educts, and in particular the corresponding monomer components, are introduced into the interior, and after that a polymerization is performed. In this reaction, a solidification takes place, so that thepolymer electrolyte 8 formed cannot escape from theopening 14. - Besides the reference electrode shown in the drawing, other embodiments are possible. In particular, the reference electrode can be combined with a measuring electrode, for instance a pH electrode, to form a single-rod measurement chain, in a manner known per se. However, still other types of electrochemical half cells can be equipped with the polymer electrolyte, for instance for amperometric measurements. The polymer electrolyte can also be used as a solid-phase electrolyte in a battery half cell.
- Production of Preferred Polymer Electrolytes
- For producing preferred polymer electrolytes, monomer solutions with a composition shown in Table 1 were mixed with a powder mixture shown in Table 2 and other additives shown in Table 3 and homogenized with cooling at 15 to 20° C. The mixtures thus obtained were introduced into electrodes with a tubular glass housing. By ensuing heat treatment of the filled electrodes, polymerization was initiated, which led to the formation of the polymer electrolytes.
TABLE 1 Monomer Solution Substance Proportion by weight Aminohydroxypropyl methacrylate (AHPMA) 8 to 12% Hydroxypropyl methacrylate (HPMA) 4 to 6% Hydroxyethyl methacrylate (HEMA) 6 to 8% Silylpropyl methacrylate ca. 0.1% N,N,N′,N′-tetramethylethlyenediamine (TEMED) ca. 0.2% Glycerine ca. 30% Powder mixture (according to Table 2) Additives (according to Table 3) Water 15 to 20% -
TABLE 2 Powder Mixture Substance Proportion by weight Potassium chloride with 2% aerosil 25 to 30% Silica gel H60 3 to 5% -
TABLE 3 Additives Substance Proportion by weight Methylene-bis-acrylamide (MBA) ca. 0.5% Ammonium persulfate ca. 0.05% 2,2′-Azo-bis(2-(2-imidazolin-2-yl)propane) ca. 0.05% dihydrochloride (WAKO 44) - The first monomer component, designated above as aminohydroxypropyl methacrylate (AHPMA), is a mixture of the two isomers 3-amino-2-hydroxypropyl methacrylate and 2-amino-3-hydroxypropyl methacrylate, which can be produced for instance by reacting glycidyl methacrylate (2,3-epoxypropyl methacrylate) with ammonia in an isomer ratio of approximately 9:1. WAKO 44 is a radical former that is used as an azo initiator for polymerization reactions. TEMED is a starter compound for the polymerization of acryl and methacryl derivatives. Silica gel and aerosil are used to improve the consistency of the polymer and to adsorb interfering substances, such as electrode poisons, from the measuring medium.
- The polymer electrolytes described above are distinguished by excellent stability to acids, water, and both polar and apolar solvents. Accordingly, these polymer electrolytes can be used in the most various types of measuring media.
- Further Exemplary Embodiments
- For particular areas of use, the properties of the polymer electrolytes can be optimized specifically, as documented by the exemplary embodiments that follow.
TABLE 4 Composition of Example 1 Proportion by Weight Monomer 3-Amino-2-hydroxypropyl methacrylate 15% 3-(Trimethyloxysilyl)propyl 1% methacrylate Cross-linking agent 2% Fillers KCl 25% Silicic acid 5% Solvents Water 22% Glycerine 30% -
TABLE 5 Composition of Example 2 Proportion by Weight Monomer 3-Diethylamino-2-hydroxypropyl 20% methacrylate 3-(Trimethyloxysilyl)propyl 1% methacrylate Cross-linking agent 5 % Fillers KCl 12% Silicic acid 8% Solvents Water 16% Glycerine 38% -
TABLE 6 Composition of Example 3 Proportion by Weight Monomer 3-Ethoxy-2-hydroxypropyl 18% methacrylate 3-(Trimethyloxysilyl)propyl 1% methacrylate Cross-linking agent 3% Fillers KCl 20% Silicic acid 5% Solvents Water 20% Glycerine 33% -
TABLE 7 Composition of Example 4 Proportion by Weight Monomer 3-Methoxy-2-hydroxypropyl 19% methacrylate 3-(Trimethyloxysilyl)propyl 1% methacrylate Cross-linking agent 3% Fillers KCl 15% Silicic acid 6% Solvents Water 21% Glycerine 35% -
TABLE 8 Composition of Example 5 Proportion by Weight Monomer 3-Methylamino-2- hydroxypropyl 14% methacrylate 3-(Trimethyloxysilyl)propyl 1% methacrylate Hydroxypropyl methacrylate 4% Cross-linking agent 5% Fillers KCl 20% Silicic acid 5% Solvents Water 15% Glycerine 36% - All the polymer electrolytes described above here have good stability to acids; other properties are listed in Table 9.
TABLE 9 Properties of the Polymer Electrolytes Investigated Example Polarity Area of Use KCl Solution 1 Strong Water; no organic Supersaturated solvents 2 Medium- Water; polar Supersaturated strong organic solvents 3 Very weak Apolar organic Supersaturated solvents 4 Medium- Polar organic Saturated weak solvents 5 Weak Polar and apolar Supersaturated organic solvents - Individually, the following properties were also ascertained. The polymer electrolyte of Example 1 is stable to water but not to organic solvents. The polymer electrolyte of Example 2 is suitable for use with water and polar solvents. The polymer electrolyte of Example 4, compared to that of Example 3, has a shorter service life. The polymer electrolyte of Example 5 is especially well suited, because of its stability, for use with any organic solvents.
- It will be appreciated by those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the invention is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced thereon.
Claims (22)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US11/797,763 US7387716B2 (en) | 2002-03-27 | 2007-05-07 | Polymer electrolyte, half cell for electrochemical measurements, and the use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10214035A DE10214035A1 (en) | 2002-03-27 | 2002-03-27 | Polymer electrolyte, half cell for electrochemical measurements and their use |
DE10214035.9 | 2002-03-27 |
Related Child Applications (1)
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US11/797,763 Division US7387716B2 (en) | 2002-03-27 | 2007-05-07 | Polymer electrolyte, half cell for electrochemical measurements, and the use thereof |
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US20030183517A1 true US20030183517A1 (en) | 2003-10-02 |
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US10/396,401 Abandoned US20030183517A1 (en) | 2002-03-27 | 2003-03-26 | Polymer electrolyte, half cell for electrochemical measurements, and the use thereof |
US11/797,763 Expired - Fee Related US7387716B2 (en) | 2002-03-27 | 2007-05-07 | Polymer electrolyte, half cell for electrochemical measurements, and the use thereof |
Family Applications After (1)
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US11/797,763 Expired - Fee Related US7387716B2 (en) | 2002-03-27 | 2007-05-07 | Polymer electrolyte, half cell for electrochemical measurements, and the use thereof |
Country Status (4)
Country | Link |
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US (2) | US20030183517A1 (en) |
JP (1) | JP4413514B2 (en) |
CH (1) | CH696007A5 (en) |
DE (1) | DE10214035A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1560019A1 (en) * | 2004-01-28 | 2005-08-03 | Mettler-Toledo GmbH | Polymeric electrolyte, half-cell for electrochemical measurements and its use |
EP1956369A2 (en) | 2007-02-08 | 2008-08-13 | Hamilton Bonaduz AG | Nano hybrid gels as polymer electrolytes based on transesterified organosiloxanes |
US20090166198A1 (en) * | 2007-12-28 | 2009-07-02 | Industrial Technology Research Institute | Reference electrode |
WO2014091083A1 (en) * | 2012-12-14 | 2014-06-19 | Åbo Akademi | A reference electrode and an arrangement for an electrochemical measurement |
Families Citing this family (12)
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US20080012014A1 (en) * | 2006-07-14 | 2008-01-17 | Jin-Seong Park | Thin film transistor, method of preparing the same, and flat panel display device including the thin film transistor |
US9017937B1 (en) * | 2009-04-10 | 2015-04-28 | Pacific Biosciences Of California, Inc. | Nanopore sequencing using ratiometric impedance |
US8986928B2 (en) | 2009-04-10 | 2015-03-24 | Pacific Biosciences Of California, Inc. | Nanopore sequencing devices and methods |
US8652779B2 (en) | 2010-04-09 | 2014-02-18 | Pacific Biosciences Of California, Inc. | Nanopore sequencing using charge blockade labels |
CN103975235A (en) | 2011-12-15 | 2014-08-06 | 梅特勒-托利多公开股份有限公司 | Reference electrode |
CN105940296B (en) * | 2014-01-31 | 2019-10-18 | 株式会社百乐 | Compare electrode internal solution, compare electrode, glass electrode and electrochemical determining device |
KR20170047659A (en) | 2015-10-23 | 2017-05-08 | 삼성전자주식회사 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery employing the same |
KR102425829B1 (en) | 2015-10-23 | 2022-07-28 | 삼성전자주식회사 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery employing the same |
KR102490866B1 (en) | 2015-10-23 | 2023-01-20 | 삼성전자주식회사 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery employing the same |
KR20170047656A (en) | 2015-10-23 | 2017-05-08 | 삼성전자주식회사 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery employing the same |
EP3619757A4 (en) * | 2017-05-04 | 2021-05-05 | Commonwealth Scientific and Industrial Research Organisation | Solid state reference electrode |
AT520779B1 (en) * | 2017-12-21 | 2020-03-15 | Erba Tech Austria Gmbh | Reference electrode for potentiometric measurement of ion concentrations |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3798750A (en) * | 1972-07-21 | 1974-03-26 | Gen Electric | Sensor and method of manufacture |
US4432366A (en) * | 1981-11-27 | 1984-02-21 | Cordis Corporation | Reference electrode catheter |
US20020193451A1 (en) * | 1999-08-18 | 2002-12-19 | Jsr Corporation | Method of chemical mechanical polishing |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9118300D0 (en) * | 1991-08-24 | 1991-10-09 | Kodak Ltd | Reference half-cell electrode |
JPH05198303A (en) * | 1992-01-21 | 1993-08-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Battery |
US5549988A (en) * | 1995-03-10 | 1996-08-27 | Motorola, Inc. | Polymer electrolytes and electrochemical cells using same |
EP1124132B1 (en) * | 2000-02-10 | 2008-12-31 | Hamilton Bonaduz AG | Polymerelectrolyte |
ATE383573T1 (en) * | 2004-01-28 | 2008-01-15 | Mettler Toledo Ag | POLYMER ELECTROLYTE, HALF CELL FOR ELECTROCHEMICAL MEASUREMENTS AND THEIR USE |
-
2002
- 2002-03-27 DE DE10214035A patent/DE10214035A1/en not_active Withdrawn
-
2003
- 2003-03-17 CH CH00426/03A patent/CH696007A5/en not_active IP Right Cessation
- 2003-03-26 JP JP2003085268A patent/JP4413514B2/en not_active Expired - Fee Related
- 2003-03-26 US US10/396,401 patent/US20030183517A1/en not_active Abandoned
-
2007
- 2007-05-07 US US11/797,763 patent/US7387716B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3798750A (en) * | 1972-07-21 | 1974-03-26 | Gen Electric | Sensor and method of manufacture |
US4432366A (en) * | 1981-11-27 | 1984-02-21 | Cordis Corporation | Reference electrode catheter |
US20020193451A1 (en) * | 1999-08-18 | 2002-12-19 | Jsr Corporation | Method of chemical mechanical polishing |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1560019A1 (en) * | 2004-01-28 | 2005-08-03 | Mettler-Toledo GmbH | Polymeric electrolyte, half-cell for electrochemical measurements and its use |
WO2005073704A1 (en) * | 2004-01-28 | 2005-08-11 | Mettler-Toledo Gmbh | Polymer electrolyte, half cell for electrochemical measurements and use thereof |
US20070020527A1 (en) * | 2004-01-28 | 2007-01-25 | Mettler-Toledo Ag | Polymer electrolyte, half-cell for electrochemical measurements, as well as the use thereof |
US7790323B2 (en) * | 2004-01-28 | 2010-09-07 | Mettler-Toledo Ag | Polymer electrolyte, half-cell for electrochemical measurements, as well as the use thereof |
EP1956369A2 (en) | 2007-02-08 | 2008-08-13 | Hamilton Bonaduz AG | Nano hybrid gels as polymer electrolytes based on transesterified organosiloxanes |
EP1956368A1 (en) * | 2007-02-08 | 2008-08-13 | Hamilton Bonaduz AG | Nano hybrid gels as polymer electrolytes |
US20090166198A1 (en) * | 2007-12-28 | 2009-07-02 | Industrial Technology Research Institute | Reference electrode |
US8187435B2 (en) * | 2007-12-28 | 2012-05-29 | Industrial Technology Research Institute | Reference electrode |
WO2014091083A1 (en) * | 2012-12-14 | 2014-06-19 | Åbo Akademi | A reference electrode and an arrangement for an electrochemical measurement |
US10094798B2 (en) | 2012-12-14 | 2018-10-09 | Abo Akademi University | Reference electrode and an arrangement for an electrochemical measurement |
Also Published As
Publication number | Publication date |
---|---|
US7387716B2 (en) | 2008-06-17 |
JP2004004011A (en) | 2004-01-08 |
US20070205098A1 (en) | 2007-09-06 |
JP4413514B2 (en) | 2010-02-10 |
CH696007A5 (en) | 2006-11-15 |
DE10214035A1 (en) | 2003-10-09 |
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Owner name: METTLER-TOLEDO GMBH, SWITZERLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:EHRISMANN, PHILIPPE;THRIER, ROLF;REEL/FRAME:014114/0315;SIGNING DATES FROM 20030507 TO 20030509 |
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Owner name: METTLER-TOLEDO AG,SWITZERLAND Free format text: CHANGE OF NAME;ASSIGNOR:METTLER-TOLEDO GMBH;REEL/FRAME:018132/0090 Effective date: 20060710 Owner name: METTLER-TOLEDO AG, SWITZERLAND Free format text: CHANGE OF NAME;ASSIGNOR:METTLER-TOLEDO GMBH;REEL/FRAME:018132/0090 Effective date: 20060710 |
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