EP2616572A2 - Anordnung und verfahren zur beeinflussung der kinetik chemischer reaktionen mittels akustischer oberflächenwellen - Google Patents
Anordnung und verfahren zur beeinflussung der kinetik chemischer reaktionen mittels akustischer oberflächenwellenInfo
- Publication number
- EP2616572A2 EP2616572A2 EP11771050.9A EP11771050A EP2616572A2 EP 2616572 A2 EP2616572 A2 EP 2616572A2 EP 11771050 A EP11771050 A EP 11771050A EP 2616572 A2 EP2616572 A2 EP 2616572A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- waves
- active surface
- fluid
- active
- acoustic waves
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonic waves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
Definitions
- the invention relates to an arrangement for influencing the kinetics of chemical reactions by means of surface acoustic waves according to claim 1 and a method according to claim 13.
- the invention relates to a method based on the use of surface acoustic waves, which in particular chemical reactions can be influenced in their course and thus the efficiency of these reactions can be increased (acceleration of the reaction processes, increased material turnover, etc.).
- the slowest reaction step determines the kinetics of the overall reaction.
- the speed of the overall reaction is therefore mainly due to the Rate determines with which the electrochemically active particles are transported to the working electrode. If this rate is insufficient, the current decreases continuously over time with constant voltage. This dependence of the speed is described in the literature (VM Schmidt: Electrochemical Process Engineering, Fundamentals, Reaction Engineering, Process Optimization, WILEY-VHC Verlag, 2004; ISBN: 9783527299584)
- This gradient is the driving force for the subsequent delivery of further electrochemically active particles to the electrode and determines the rate at which the reaction proceeds. It is known from the literature that the use of ultrasound can influence the forming boundary layer and thus the chemical reaction. As a rule, high-power ultrasound in the frequency range from 20 kHz to 2 MHz is applied to the electrode with the aid of ultrasonic horns (so-called sonotrodes), but the sonotrode must be brought directly to or in the vicinity of the electrode, usually by immersing the sonotrode happens in the electrolyte.
- the problem underlying the invention is to provide an arrangement and a method which make it possible to influence chemical reactions in the simplest and most effective manner possible.
- reaction vessel in which at least one active surface, which is at least partially in contact with a fluid, is arranged
- a chemical reaction at the at least one active surface or a physical process occurring there is influenced, in particular accelerated, by the surface waves in the at least one active area and / or by the volume sound waves in the fluid.
- the means for generating surface waves comprise an acoustic transducer which converts an electrical signal into vibrations which are transmitted to the active surface.
- the transducer is an interdigital transducer with which, e.g. Even in active surfaces of a non-piezoelectric material surface acoustic waves can be excited.
- the turnover is also increased due to the increased mixing and the ultrasound-induced formation of radicals;
- Another field of application of the arrangement according to the invention is polymer chemistry.
- an improved emulsion of substances needed for polymerization reactions can be achieved.
- the formation of thin polymer films on the active surface can be prevented (e.g., on an electrode surface) affecting the further electrode reaction.
- the catalytic activity could be increased during a reaction.
- the type of surface waves excited in the active area depends in particular on the thickness of the substrates used and the acoustic wavelength.
- surface waves of the Rayleigh-wave type can be excited, in particular with thick substrates, i. if the substrate thickness (the thickness of the active area) is greater than the acoustic wavelength.
- Surface waves of the lamb wave type can be excited with thin substrates, whereby the substrate thickness must be smaller than the acoustic wavelength.
- the bulk waves are thus radiated into the liquid at the Rayleigh angle, thereby reducing the energy of the remaining surface acoustic wave.
- An "active surface” is to be understood in particular as meaning the surface of a solid (for example of metal, glass, plastic, ceramic) on or in whose immediate vicinity a chemical reaction or a physical process takes place and / or is excited or influenced can.
- the fluid disposed within the reaction vessel may be, for example, gases, but also liquids which may contain dissolved organic or inorganic substances (such as salts). Such liquids would be, for example, water, ammonia, THF, acetone, acetonitrile, DMSO, hexane, toluene or benzene. Alternatively, the fluid may also be a melt of organic or inorganic substances or metals.
- the reaction vessel has a bottom, wherein an opening for filling in the fluid is present in relation to the bottom. From the bottom is a side wall of the reaction vessel from which limits together with the bottom of an inner volume of the reaction vessel.
- the active area is e.g. at least partially in the internal volume of the reaction vessel.
- the arrangement for performing a chemical reaction further comprises a means for generating surface acoustic waves, which is suitable to excite surface acoustic waves within the at least one active surface, wherein at least a portion of the surface waves excited in the at least one active surface are transformed into bulk acoustic waves (volume sound waves ) is converted within the fluid.
- An increased mass transfer or heat exchange or increased mixing or a change in the reaction mechanisms are possible, for example.
- the means for generating surface acoustic waves comprise at least one transmitter.
- the transmitter is designed in particular in the form of an interdigital transducer.
- the means for generating surface acoustic waves is arranged on a side facing the reaction vessel ("mounting side") of the at least one active surface, this side of the at least one active surface having, for example, the smallest distance between the reaction vessel and the at least one active surface, ie this side has, in one example, a smaller distance to the reaction vessel than a side facing away from the mounting side of the active surface.
- an electrically insulating substrate extends on the side facing the reaction vessel (the mounting side) of the at least one active surface.
- the substrate may be formed in the form of a portion of a wall of the reaction vessel.
- the means for generating surface acoustic waves is arranged on a side of the electrically insulating substrate which faces away from the at least one active surface and generates surface acoustic waves in the substrate.
- an intermediate layer to be arranged between the substrate and the at least one active surface, via which at least part of the surface wave excited in the substrate couples into the at least one active surface.
- the active surface is partially in contact with the fluid and the surface acoustic wave generating means is on the active surface arranged in the area that is not in contact with the fluid.
- a temperature control means is arranged on the reaction vessel, which is suitable for increasing or decreasing the temperature of the at least one active surface and / or of the fluid.
- reaction vessel is disposed within a housing, wherein on the housing, a pressure control means is provided, which is adapted to set a pressure within the housing or within the reaction vessel above or below the atmospheric pressure. This can be done for example by means of conventional high-pressure pumps or vacuum pumps.
- a second active surface is arranged within the reaction vessel, wherein the fluid can be arranged between the first and the second active surface.
- the means for generating surface acoustic waves in the first and / or the second active surface excite surface acoustic waves, wherein at least a part of the surface waves excited in the first and / or the second active surface are reflected in bulk acoustic waves (volume sound waves) in the one between the two active surface fluid is converted.
- the first and the second active surface is in each case designed as an electrode, which can be connected to one another via voltage sources.
- the fluid may be formed as an electrolyte.
- the means for generating surface acoustic waves in the first and / or the second electrode generates surface acoustic waves, wherein at least part of the surface waves applied in the first and / or the second electrode are in bulk acoustic waves (volume sound waves) in the electrolyte located between the electrodes is converted.
- a chemical reaction in the electrolyte is influenced by the surface waves in the first and / or the second electrode and / or the volume sound waves in the electrolyte. In particular, the chemical reaction is accelerated.
- the means for generating surface acoustic waves comprise at least one transmitter, as mentioned, in particular in the form of an interdigital transducer.
- the transmitter is arranged on a side of the first electrode facing away from the electrolyte.
- an electrically insulating substrate may extend on a side of the first electrode facing away from the electrolyte.
- the electrically insulating substrate may be provided in particular in the form of a portion of a wall of a reaction vessel. It can be provided that the transmitter is disposed on a side facing away from the first electrode of the substrate and generates surface acoustic waves in the substrate.
- the substrate may be an intermediate layer via which at least a portion of the surface waves excited in the substrate couples into the first electrode.
- the invention also relates to a method for influencing the kinetics of chemical reactions by means of surface acoustic waves, comprising the steps Providing at least one active area;
- Generating surface acoustic waves in the at least one active area wherein at least a portion of the surface waves excited in the at least one active area is converted into bulk acoustic waves within the fluid, such that a chemical reaction preceding the fluid or a preceding physical event is influenced, in particular accelerated, by the surface waves in the at least one active surface and / or the volume sound waves in the fluid.
- surface acoustic waves are transmitted directly to the chemically active surface (for example an electrode) and specifically influence the reaction there.
- the sound is introduced into the reaction system from the outside, so that the sound transducers which generate the surface waves, including the associated electronics, do not come into direct contact with the chemically active substances or impair any built-in parts of the experimental setup.
- the process according to the invention is intended to be used primarily in electrochemical processes, but is also suitable for other chemical reaction processes.
- the method is flexibly adaptable to different experimental setups, so that existing chemical plants can remain unchanged.
- the speeds can be increased.
- surface acoustic waves are transmitted directly to the chemically active surface (for example an electrode), in order to specifically influence the reaction there.
- the sound is ideally introduced from the outside into the reaction system, so that the sound transducers which generate the surface waves, including the associated electronics, do not come into direct contact with the chemically active substances or impair any built-in parts of the experimental setup.
- the surface waves to decouple in contact with liquids as a bulk wave and vice versa when impinging on solid substrates and re-generate a surface wave there, it is possible to transfer the sound directly to one or more chemically active surfaces. It is not necessary to introduce a sonotrode into the medium, as is the case with most sonokinetic methods, but it becomes a piezoelectric one Interdigital transducer outside the reaction vessel, the experimental setup or applied externally to the electrode, which generates the surface waves there. Use with gases is also possible.
- the new in the inventive method and the arrangement according to the invention consists on the one hand that the sound irradiation in the reaction system is not done via introduced into the system components (eg sonotrodes), but the sound from the outside to the system (eg on the wall of the reaction vessel, or directly to the electrode) mounted special piezoelectric interdigital transducer, which stimulate surface acoustic waves occurs. That is, an internal reaction can be influenced by an externally mounted component, which could already be shown in individual experiments by a strong increase in the reaction rate, as already explained above.
- the system components eg sonotrodes
- the sound irradiation is not diffusely directed to the electrode or other chemically active surface, as is the case with an ultrasonic horn; Rather, the sound is directed, in particular via effects such as mode conversion and reverse mode conversion, at least substantially directly to the electrode, where again a surface wave is generated.
- effects such as mode conversion and reverse mode conversion, at least substantially directly to the electrode, where again a surface wave is generated.
- the method according to the invention has the advantage that it can be flexibly adapted to different constructions and furthermore it is not fixed to a very specific area of chemistry or a very specific chemical process but can be applied in a variety of ways. The same is true for the arrangement according to the invention.
- a chemical reaction or a physical process within a reaction vessel is influenced, in particular accelerated, by targeted excitation of surface acoustic waves within at least one or more active surfaces and / or volume sound waves generated in a fluid. It is not necessary that the means for generating surface acoustic waves within the reaction vessel, in particular within the reaction fluid must be attached. This avoids that the means for generating surface acoustic waves is attacked by particularly aggressive chemical processes or such built-in parts affect the experimental design.
- the arrangement according to the invention and the method according to the invention are characterized in that a targeted and controlled excitation of the active surfaces takes place by means of surface acoustic waves, e.g.
- a targeted and controlled excitation of the active surfaces takes place by means of surface acoustic waves, e.g.
- the significantly lower space requirement of the device according to the invention and the method according to the invention makes it possible to modify the chemical reactions better than a "sonication" over a wide area by means of, for example, an ultrasonic horn.
- the method according to the invention (correspondingly also the arrangement according to the invention) can be used in particular in electrochemical processes, but it is also suitable for other chemical reaction sequences. It can be used in almost all areas of chemistry, where liquid media and Interfaces in the game are, as already indicated above, for example
- Electrochemistry e.g., electroplating, accumulator industry, etc.
- the process can be flexibly adapted to different experimental setups so that existing chemical plants can essentially remain unchanged.
- Figure 1 is a schematic view of a first embodiment of the invention
- Figure 2 is an illustration of the current-voltage curve of an inventive
- FIG. 3 is an illustration of a current-voltage curve when acoustic is excited
- Figure 4 shows a schematic structure of a second embodiment of the invention
- Fig. 5 is a modification of Fig. 4.
- FIG. 6 shows a diagram of a current curve whose influence shows the excited surface waves according to the invention.
- FIG. 1 shows an embodiment for carrying out a chemical reaction in a schematic view.
- the arrangement has a reaction vessel 8, in which a first and a second active area in the form of a first electrode 1 1 and a second Electrode 12 are arranged.
- a fluid in the form of an electrolyte 31 is arranged between the first and the second electrode 1 1, 12.
- the arrangement has a arranged on a side wall 81 of the reaction vessel 8 means for generating surface acoustic waves - here an interdigital transducer 4 -, wherein the interdigital transducer 4 on the side (Au JOseite) of the side wall 81 of the reaction vessel 8 is mounted, of the 1 1 facing away from the first electrode.
- the interdigital transducer 81 surface waves 6 are excited in the side wall, wherein it is the excited surface waves in particular Lamb waves, which are then excited when the thickness of the substrate is smaller than the wavelength.
- the reaction vessel 8 which is e.g. consists of an electrically insulating substance (for example, a reaction vessel made of glass) produces surface waves.
- the first electrode 1 1, on which a diffusion boundary layer 31 1 is formed connected via an intermediate layer 51.
- This intermediate layer 51 may consist, for example, of a liquid or a gas. It is also conceivable that the intermediate layer 51 is formed by the electrolyte 31.
- the surface acoustic waves excited in the sidewall 81 partially couple at the Rayleigh angle into the intermediate layer 51 (mode conversion) and then vice versa again into the electrode 11, wherein surface waves 6 'are also excited in the electrode 11.
- the excited surface wave 6 thus couples into the intermediate layer 51 and generates in the intermediate layer 51, so to speak, a volume sound wave (small arrows), which in turn can be coupled into the first electrode 1 1, to there again to produce a surface acoustic wave 6 '.
- the process of a mode conversion takes place again, that is, the surface wave 6 'in the electrode 1 1 couples at a certain angle ( Rayleigh angle) in the surrounding medium, ie the electrolyte 31, and thus also in the diffusion boundary layer 31 1 and generates a volume sound wave 7 in the liquid medium.
- a certain angle Rayleigh angle
- volume sound wave 7 Due to the interaction of the sound wave (volume sound wave 7) with the diffusion boundary layer 31 1, the chemical reactions taking place there are positively influenced. Once the surface acoustic wave 6 'has been coupled out into the electrolyte 31, the sound wave (volume sound wave 7) is coupled in again into the second electrode 12, which again generates the excitation of surface waves 6 "there.
- Figure 2 shows the current-voltage curve of an inventive arrangement comparable to Figure 1 in comparison with a standard arrangement (without generating surface sound waves).
- the experimental set-up consisted of a Cu / Au electropolishing cell in which material was to be removed from a copper plate by applying a DC voltage.
- the copper in this case acted as anode (corresponds to electrode 1 1 in Figure 1), the cathode was made of a pure gold plate (corresponding to electrode 12 in Figure 1).
- the polishing cell itself is a beaker in which a copper sheet has been attached to the inner bottom. At about 1 cm from the copper sheet, a gold sheet was positioned parallel to the copper sheet.
- the electrolyte 31 was a solution of nitric acid (65%) and methanol in a mixing ratio of 1: 2, which is filled in the beaker, so that the gold sheet is covered with it.
- FIG. 2 shows the course of an electropolishing curve with and without ultrasound entry (SAW).
- SAW ultrasound entry
- FIG. 3 shows a current-voltage curve in an electropolishing test when surface acoustic waves 6 are excited via an interdigital transducer 4 mounted externally on the reaction vessel 8 in accordance with the arrangement according to the invention.
- the illustrated current-voltage characteristic curve over the duration of a complete electropolishing experiment likewise shows once again that the current consumption can be increased by exciting surface acoustic waves 6.
- FIG. 4 describes a further embodiment of the arrangement according to the invention.
- Another alternative is the excitation of surface waves 6 directly on the first electrode surface 1 1, as shown schematically in Figure 4.
- the interdigital transducer 4 used to generate the surface waves 6 is arranged elsewhere on the electrode 11.
- the electrode 1 1, on which the surface waves run 6, depends freely and, for example, attached only via a clamping connection to the reaction vessel 8 in the electrolyte 31st It is not attached to the bottom of the reaction vessel 8, for example.
- the anode (first electrode 1 1) immersed in the electrolyte liquid (electrolyte 31) the mode conversion (as already described in Figure 1) of the surface acoustic waves 6 and thus a decoupling of a portion of the sound energy (in the form of a Volume sound wave 7) in the surrounding medium (electrolyte 31) and thus also in any existing diffusion layer (not shown here for reasons of clarity).
- the chemical reaction at the surface of the first electrode 1 1 is accelerated and the current flow is increased, which has already been experimentally confirmed by first measurements (see FIG. 5).
- a re-coupling of the volume sound wave 7 in the second electrode 12 can be carried out, wherein again a surface wave is excited within the second electrode 12.
- the region marked A in this exemplary embodiment describes the region in which increased chemical reactions take place on the surface of the first or second electrode 1 1, 12, which is caused by the coupling or coupling in of the surface waves 6.
- Fig. 5 shows a modification of the arrangement of Fig. 4.
- an additional (e.g., metallic) plate 100 is provided which is at least approximately parallel to the upper portion of the first electrode 11.
- the plate 100 has e.g. one with the first electrode 1 1 comparable or identical thickness.
- This acoustic waveguide performs volume sound waves which propagate in an electrolyte-filled gap between the first electrode 1 1 and the plate 100 and caused by conversion of the surface acoustic waves 6 excited by the transmitter 4 in the first electrode 1 1.
- the leadership of the volume sound waves is generated in particular by the fact that both the first electrode 1 1 and on the plate 100, a reflection of the volume sound waves takes place (solid zigzag line). As a result, excessive energy loss of the volume sound waves excited in the electrolyte before reaching the second electrode 12 is counteracted.
- the plate 100 is insofar as far as possible brought up to the second electrode 12, approximately to the curvature of the first electrode 11. It is also conceivable that the plate 100 extends beyond the curvature of the first electrode 1 1 and also has a curvature parallel to the curvature of the first electrode and corresponding to a portion which extends at least approximately parallel to a bottom of the reaction vessel.
- the plate 100 can be at least approximately at the potential of the first electrode 1 1.
- FIG. 6 shows a current curve of an electropolishing test, which shows the influence of a sound entry by actuation of an interdigital transducer 4.
- FIG. 6 shows the current development on a time scale. It can be observed up to a time of about 7 minutes, a steady increase in current strength.
- switching on B of the interdigital transducer 4 there is a sudden increase in the current intensity, which again drops sharply when switching off C of the interdigital transducer 4, that is to say removing the sound input, and in turn increases abruptly when it is switched on again.
- switching off again C the current drops again.
- FIG. 6 clearly shows that the current flow is increased by an arrangement according to the invention, and consequently the chemical reaction at the electrode surface is also accelerated.
- the arrangement according to the invention thus enables a targeted acceleration of the electrochemical reaction.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010040996 | 2010-09-17 | ||
| PCT/EP2011/066251 WO2012035172A2 (de) | 2010-09-17 | 2011-09-19 | Anordnung und verfahren zur beeinflussung der kinetik chemischer reaktionen mittels akustischer oberflächenwellen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2616572A2 true EP2616572A2 (de) | 2013-07-24 |
| EP2616572B1 EP2616572B1 (de) | 2019-07-10 |
Family
ID=44897705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11771050.9A Active EP2616572B1 (de) | 2010-09-17 | 2011-09-19 | Anordnung und verfahren zur beeinflussung der kinetik chemischer reaktionen mittels akustischer oberflächenwellen |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP2616572B1 (de) |
| WO (1) | WO2012035172A2 (de) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5865894A (en) * | 1997-06-11 | 1999-02-02 | Reynolds Tech Fabricators, Inc. | Megasonic plating system |
| CA2343440A1 (en) * | 2000-07-13 | 2002-01-13 | G. Alan Thompson | Ultrasonic process for autocatalytic deposition of metal |
| US6368482B1 (en) * | 2000-09-19 | 2002-04-09 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration, Washington, Dc (Us) | Plating processes utilizing high intensity acoustic beams |
| US6573183B2 (en) * | 2001-09-28 | 2003-06-03 | Agere Systems Inc. | Method and apparatus for controlling contamination during the electroplating deposition of metals onto a semiconductor wafer surface |
| US7040332B2 (en) * | 2003-02-28 | 2006-05-09 | Lam Research Corporation | Method and apparatus for megasonic cleaning with reflected acoustic waves |
| US7119019B2 (en) * | 2004-03-31 | 2006-10-10 | Intel Corporation | Capping of copper structures in hydrophobic ILD using aqueous electro-less bath |
| DE102007043563A1 (de) * | 2007-09-13 | 2009-03-19 | Bell, Guido, Dr. | Ätzen, Galvanisieren, Reinigen und Photolackentwickeln mit Megasonic-Unterstützung |
| RU2353713C1 (ru) * | 2008-02-21 | 2009-04-27 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Электролит кадмирования и способ нанесения кадмиевых покрытий на металлические изделия |
-
2011
- 2011-09-19 EP EP11771050.9A patent/EP2616572B1/de active Active
- 2011-09-19 WO PCT/EP2011/066251 patent/WO2012035172A2/de not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2012035172A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012035172A2 (de) | 2012-03-22 |
| WO2012035172A3 (de) | 2012-12-27 |
| EP2616572B1 (de) | 2019-07-10 |
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