WO1999053121A1 - Automated chemical process control system - Google Patents
Automated chemical process control system Download PDFInfo
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- WO1999053121A1 WO1999053121A1 PCT/US1999/007918 US9907918W WO9953121A1 WO 1999053121 A1 WO1999053121 A1 WO 1999053121A1 US 9907918 W US9907918 W US 9907918W WO 9953121 A1 WO9953121 A1 WO 9953121A1
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- WIPO (PCT)
- Prior art keywords
- chemical
- control system
- sample
- analysis
- predetermined
- Prior art date
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Classifications
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
- G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N35/10—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
- G01N35/1095—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices for supplying the samples to flow-through analysers
- G01N35/1097—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices for supplying the samples to flow-through analysers characterised by the valves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
- B01F23/59—Mixing systems, i.e. flow charts or diagrams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/80—Forming a predetermined ratio of the substances to be mixed
- B01F35/82—Forming a predetermined ratio of the substances to be mixed by adding a material to be mixed to a mixture in response to a detected feature, e.g. density, radioactivity, consumed power or colour
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/56—Labware specially adapted for transferring fluids
- B01L3/565—Seals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
- B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
- G01N31/164—Determining the equivalent point by means of a discontinuity by electrical or electrochemical means
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
- G05D11/00—Control of flow ratio
- G05D11/02—Controlling ratio of two or more flows of fluid or fluent material
- G05D11/13—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means
- G05D11/135—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means by sensing at least one property of the mixture
- G05D11/138—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means by sensing at least one property of the mixture by sensing the concentration of the mixture, e.g. measuring pH value
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
- G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
- G05D21/02—Control of chemical or physico-chemical variables, e.g. pH value characterised by the use of electric means
Definitions
- This invention relates generally to chemical processing systems, and more particularly, to a system that monitors and replenishes automatically a liquid volume in a chemical processing system, such as a chemical bath.
- a chemical processing system such as a chemical bath.
- the invention described herein relates to an automatic on-line chemical bath control system which, for example can be used as an automatic chemical bath control system for a chemical mechanical planarization processes.
- CMP Chemical mechanical planarization or polishing
- a typical CMP process utilizes a slurry of an abrasive in a diluent, which is, in some cases, an oxidizer. Maintaining the slurry quality is essential to maximizing device yields.
- Dynamic measurements of slurry properties such as pH, specific gravity, percent solids by weight, or slurry particle size distribution, should be made to ensure the that the slurry is stable. That is, the slurry must be resistant to settling and agglomeration, and be free of contaminants, such as slurry particle aggregates, foreign particles, adsorbed carbon dioxide, and ionic contaminants.
- monitoring and measuring of the slurry properties and chemical component assays can be done on-line, or off-line. While on-line measurements provide real-time data, many analytical instruments are not easily adapted to on-line sampling thereby causing users to opt for off-line analytical techniques. In addition, on-line analytical instruments require frequent maintenance and calibration for proper operation. There is, therefore, a need in the art for improved automatic on-line CMP process control.
- CMP chemical bath should be monitored and replenished, as required.
- Semi-Sperse® W2000 a tungsten CMP slurry manufactured by Cabot Corporation, Aurora, IL
- oxidizer hydrogen peroxide
- monitoring and replenishment should be on-line and automated.
- Weight percent of hydrogen peroxide in Semi-Sperse® W2000 can be tested using reduction titration with an oxidizing agent such as cerium sulfate (Ce(SO 4 ) 2 ) or potassium permanganate (KMnO .
- an automated titration/control system must be as or more reliable, accurate, and repeatable than manual titration methods.
- platinum ORP, gold ORP, thermometric, or colorimetric sensors may be used to detect a differential endpoint (i.e., the inflection point).
- a still further object of this invention is to provide prevent wastage of the unused chemical under test by providing the ability to restore same to the tank from which it was drawn.
- An additional object of this invention is to provide a chemical analysis system that accommodates a wide range of sample volumes and concentrations, thereby increasing system versatility.
- Yet another object of this invention is to provide a chemical analysis system that provides a reference cell having an extended term zero potential electrical connection to the solution, without suffering the ion migration problems associated with a gel-filled reference cell electrolyte, or the use of a flow-limiting, electrolyte preserving, plug of porous wood, ceramic, or plastic installed at the tip.
- Another object of this invention is to provide a chemical processing system that accurately maintains the concentration of blended and held mixtures by measuring the level of the mixtures and calculating their respective volumes, then adjusting replenishment quantities that have been determined by analysis, or in response to the passage of time, in response to solution tank volumes.
- Still another object of this invention is to provide a chemical control system wherein there is provided level monitoring, chemical analysis, and peroxide control in blend and distribution (or hold) tanks used in CMP slurry preparation.
- An object of this invention is to provide a chemical processing system having electronic communication of data containing information related to analysis results, status, errors, replenishment quantities, etc. with a remote host operator interface. GENERAL INTRODUCTION TO THE SYSTEM OF THE PRESENT INVENTION.
- This invention which provides, in a titration analyzer embodiment of the present invention, a microprocessor-based system that performs a variety of wet chemical analysis procedures, such as direct pH measurement or pH, ORP or colorimetric titrations.
- the analyzer of the present invention also performs sample retrieval, sample preparation, cleanup, data manipulation, auto-calibration, and diagnostics. -5-
- the analyzer performs a series of tests without the need for further instruction by a human operator. Each analysis is automatically replicated and the results of the analyses are statistically evaluated to assure the final reported result is repeatable to within a user-specified tolerance. The final result is then validated by the computerized manager by performance of a series of range and trend checks.
- the computerized manager enables the user to view and modify analysis configuration parameters, such as sample volume, dilution volume, and tolerance. Additionally, the computerized manager affords the user has the flexibility to operate the various valves, syringes, and mixer(s), and to obtain electrode and detector readings. These devices will be described in detail below.
- an on-line automatic analyzer eliminates the need for manual analysis and provides analytical accuracy and repeatability that surpasses manual methods and conventional instruments.
- the inventive system operates, in some embodiments of the invention, in combination with a replenishment system, whereby control over process baths, as well as the monitoring thereof, are automated.
- the analyzer of the present invention draws samples automatically from multiple process baths and performs chemical analysis of the process chemistries.
- the results of the analysis are delivered to a manager system.
- Self calibration and diagnostic routines are programmed within the analyzer to ensure consistent and reliable system performance.
- the analyzer of the present invention includes a precision replenishment system that receives chemical addition instructions from the manager system.
- the chemical addition instructions are based on analytical results, amp-minutes, process time (time in bath), or on manually entered operator commands.
- the manager system identifies to the replenisher control system the particular pump to be activated, and the particular valve that will be opened or closed. Precision flow sensors are used to monitor the volume being added.
- the system is -6- designed to maintain inventories of chemical stocks and report on chemical usage by process batch.
- a digital keypad is employed to enable remote control over the system operation.
- the PC interface is a MICROSOFT Windows®-based system that employs graphical icons to simplify operation of the system.
- the computerized manager communicates with all of the other modules that will be described herein via an RS-422 interface, and processes incoming data according to predetermined operator settings. Commands issued by the computerized manager initiate control functions and operator alarms.
- the computerized manager includes a database that provides a history of all parameters monitored by the system. Such historical information can be used to generate reports that are available from the computerized manager. Thus, at any time, for any time frame, and for any parameter, bath, chemical, or module, an operator can print a variety of tables, graphs, charts, and status reports.
- the analyzer of the present invention performs three basic functions, specifically sampling, analysis, and cleanup. Included in these functions are diagnostics, auto- calibration, and calculations.
- SAMPLING Sampling retrieves liquid from a tank, sample loop, or grab sample receptacle and delivers it to the analysis cell.
- a sample syringe is cycled to pump the sample in and purge any other liquid.
- Several cycles of sample are delivered to the reaction cell beaker to ensure that the sample is representative of the liquid in the tank.
- both a timer and a sample arrival detector are used to verify that the sample arrived within an adequate period of time for the analysis to proceed.
- the beaker is thoroughly cleaned before the final sample dose is dispensed.
- the liquid either is pushed into the analysis beaker by the pressure in the sample loop or drawn in by an eductor.
- a titration analysis is performed after the sample has been delivered to the cell.
- a titration analysis may be performed with an optional conditioning reagent delivered, in one embodiment of the invention, by gravity through a solenoid valve. Titrant is conveyed by a syringe that is actuated under the control of a stepper motor. Titrant is continuously added while analog readings are taken at predetermined intervals in order to find the endpoint. Once the endpoint is found, the beaker is cleaned and the test is repeated until the results agree within a user-specified tolerance. In a practicable embodiment of the invention, a minimum of three replicates is required, with a maximum of nine being permitted. As soon as the results are satisfactory for non-continuous analyses, the analyzer performs a thorough cleanup to avoid cross contamination.
- Bottled samples may be presented to the analyzer for analysis at the grab sample sipper port.
- the sample concentration should be within the specification range (alarm limits) of the parameter being tested.
- the pH calibration is performed before an analysis using the pH electrode if a user specified time has elapsed since the last pH calibration.
- the calibration uses two pH buffers to determine the slope and the offset of the pH electrode. A stable reading is obtained on one buffer, then the beaker is cleaned and a reading is taken on the other.
- the slope value is transmitted to the automated manager to enable the operator to know the condition of the electrode.
- the slope and offset values are retained by the analyzer -8- to convert voltage readings to pH values.
- the frequency of calibration is set through the analysis configuration table register titled "Hours calibration valid.”
- Electrode sensitivity calculated as a ratio of actual response to ideal response, is reported after each analysis and can be viewed at the automated manager with the other analyzer parameters.
- Ion selective electrodes are used to measure a variety of analytes using the method of standard addition.
- known amounts of a standard solution having a known concentration of analyte are added sequentially to a solution of unknown concentration.
- the electrode potential is measured after each addition.
- the increased signal produced by an ion selective electrode permits determination of the quantity of analyte in the original sample by extrapolation back to the point of zero analyte concentration.
- the method of standard addition is accurate and reproducible. It avoids the requirement of preparing calibration standards having a background solution (matrix) identical to that of the unknown.
- the underlying assumption in using a standard (known) addition is that the matrix has the same effect on added analyte as it has on the original analyte in the unknown sample.
- the turbidity sensor is used to measure 1) concentrations that are proportional to turbidity and 2) titrations that have turbid (cloudy) endpoints
- the proportional method requires calibration to establish the correlation between turbidity and concentration Sulfate measurement (in the form of barium sulfate) is an example this type of measurement
- turbid endpoint titration is that used for cyanide in plating solutions
- the method is to titrate a solution of unknown cyanide concentration with silver nitrate
- additional silver ion combines with iodide indicator to form a cloudy precipitate in the beaker
- This cloud is detected by the turbidity sensor, signaling the endpoint of the titration
- the turbidity probe does not require calibration except possibly when the probe is replaced This is due to the fact that the titration is looking for a relative change and not an absolute value
- the resistors associated with the probe are set so as to provide ample sensitivity for detecting even a slight turbidity
- the titration can be tuned to match what an operator would first observe as the endpoint
- the endpoint detection can be set anywhere from nearly invisible turbidity to very cloudy SUMMARY OF THE CLAIMED INVENTION
- a chemical control system for a chemical solution having predetermined chemical constituents
- an analyzer determines the proportion of one of the predetermined chemical constituents in the solution
- a precision analyzer sample delivery arrangement delivers to the analyzer a sample of the liquid chemical Information relative to the determination by the analyzer of the proportion of at least one of the predetermined chemical constituents in the liquid chemical to be delivered is received by a controller
- the controller may be implemented as a microcomputer
- a replenisher that is responsive to the controller dispenses a controlled quantity of the predetermined chemical constituent
- the controlled quantity of the -10- predetermined chemical constituent is delivered to a tank or container that holds the chemical solution.
- the analyzer is a titrater system. Certain characteristics of the sample are monitored by one or more sensors or electrodes in response to the addition of certain reagents.
- the analyzer includes, in certain embodiments, a reaction cell for receiving a sample of the liquid chemical from the precision analyzer sample delivery arrangement.
- the reaction cell is a glass beaker.
- the sensor may be any one or more of a pH electrode, a ORP electrode or an ion selective electrode, or a turbidity sensor
- the present invention is capable of monitoring a slurry.
- one of the predetermined chemical constituents in the slurry is H 2 O 2 .
- Chemical delivery is effected via a global loop that distributes the chemical solution in the plant.
- the global loop may be pressurized.
- the aforementioned controller is provided with a display in certain embodiments fur displaying infnrmation tl responsive to ih ⁇ determination made by the analyzer.
- the display may display information related to predetermined parameters of the chemical delivery system, diagnostic conditions of the chemical delivery system, a history of replenishment operations, a history of system faults, information relating to the calibration of the chemical sensors, the amount of chemical in the chemical distribution arrangement, as well as a plurality of additional system parameters and their history.
- the liquid level in each source tank is monitored by monitoring the head pressure of a gas, such as N 2 , that is delivered from a pressure regulator through an orifice, and out of a tube that is immersed in the source tank.
- a gas such as N 2
- the pressure of the monitoring gas past the orifice is responsive to the liquid chemical level.
- the pressure of the monitoring gas is maintained in nominally between approximately one and fifteen psi, and preferably between two and ten psi. -11-
- the precision analyzer sample delivery arrangement includes an eductor for drawing a sample to the analyzer.
- the eductor creates a negative pressure in the sample line.
- the analyzer is cleared by a purge system.
- the purge system includes a gas purge valve that controls the pressurized purge gas for clearing the analyzer.
- certain embodiments include a rinse solvent purge valve that controls the flow of a rinse solvent for clearing the analyzer.
- the rinse solvent may be arranged to clear the gas purge valve, in addition to the analyzer.
- a chemical delivery system for a chemical solution having a predetermined chemical constituent includes a precision analyzer sample delivery arrangement that delivers a sample of a precise quantum of the liquid chemical.
- the precise sample is received in a reaction cell, and a precise quantity of a predetermined reagent is delivered to the reaction cell by a precision analyzer reagent delivery arrangement.
- a sensor measures a characteristic of the liquid chemical typically during the addition of a reagent.
- a controller receives information relative to the actual characteristic of the liquid chemical measured by the sensor and stores same for subsequent analysis. The data is then used by the controller to control a replenisher that adds a controlled quantity of the predetermined chemical constituent to the source of the liquid chemical.
- the sample of the chemical solution is delivered to the reaction cell via a sample line, and there is provided a detection arrangement for detecting the presence of the liquid chemical in the line.
- the sensor constitutes a proximity or optical sensor arranged near the sample line. This sensor, therefore, provides to the controller indication of the availability of the liquid chemical.
- the precision analyzer sample delivery arrangement constitutes a syringe.
- the syringe is operated by a controllable driver arrangement which includes a drive motor and controlled circuitry therefore.
- the drive motor is of the known stepper type. -12-
- the reaction cell and the sample lines are cleared by a clean up arrangement that employs a purge gas.
- the clean up arrangement employs a rinse solvent.
- the rinse solvent which may be water is applied in certain embodiments of the invention in the form of bursts which maximize the rinsing effect.
- the clean up arrangement additionally cycles the sample syringe until it is cleared of the prior sample.
- a method of analysis of the chemical solution in a tank having a first chemical composition includes the steps of: delivering a sample of the chemical solution having the first chemical composition to an analysis cell; performing a titration analysis on the chemical solution having the first chemical composition that has been delivered to the analysis cell, said step of performing a titration analysis including the further steps of: controlling a syringe to convey a titrant to the chemical solution having the first chemical composition that has been delivered to the analysis cell; and analyzing a predetermined chemical characteristic of the chemical solution; determining an end point of the titration analysis; and conducting a cleanup procedure.
- the step of delivering includes the further step of delivering a predetermined sample quantity of the chemical solution having the first chemical composition to the analysis cell.
- the step of delivering includes the step of varying a rate at which the step of performing a titration analysis is conducted. This step of varying is responsive to the step of determining an endpoint of the titration analysis. In a first phase, a titration analysis is conducted in inverse proportion to a rate of change of a monitoring signal. However, as the endpoint of the titration analysis is approached, the rate of delivery of titrant is changed.
- the titrant is delivered -13- at a maximum possible speed without delivering more than the reaction can consume and without overshooting the endpoint.
- the system switches to a second phase.
- the rate of titrant addition is fixed and rather slow, and the sensor response is allowed to change freely through the inflection point. This is done to favor accuracy over speed since changing speed while near the endpoint has been found to affect or shift, the titration results somewhat.
- the step of delivering includes the step of purging from a sample loop all liquid associated with a prior sample. In this manner, the subsequent sample to be delivered will be representative of the current content of the liquid chemical being distributed.
- the step of delivering includes a further step of detecting the delivery of the sample of the chemical solution having the first chemical composition to the analysis cell.
- This step is effected as previously described using a proximity or optical sensor, in certain embodiments. Also, the delivery of the sample is timed. If the sample fails to become available within a predetermined maximum period of time, a false conditioned is announced.
- the step of performing a titration analysis includes the step of delivering a conditioning reagent.
- a conditioning reagent is effected via a controlled gravity feed arrangement.
- the step of controlling a syringe to convey a titrant includes, in certain embodiments, controlling a stepper drive arrangement that is coupled to the syringe.
- controlling a stepper drive arrangement that is coupled to the syringe.
- the steps of monitoring a predetermined chemical characteristic of the chemical solution and determining an endpoint of each titration analysis are repeated. Such steps are repeated until it is determined that the result of the titration analysis is established within -14 - predetermined parameters to be itself repeatable. In one embodiment, these steps are conducted approximately between three and nine times.
- a step of conducting a clean up procedure that includes the step of forcing an air purge through a filter through which was flowed the chemical solution having the first chemical composition. All sample lines and the reaction cell are also purged, in certain embodiments. Additionally, the sample syringe is cycled until it is cleared of the prior sample. In one embodiment, the pressure of the purge gas is monitored, and an error warning is issued if such pressure falls below a predetermined pressure. Additionally, a rinse solvent which may be water, is caused to flow through the filter and the associated sample lines.
- the step of calibrating a pH electrode Prior to performing the step of performing a titration analysis, there is provided the step of calibrating a pH electrode.
- This step of calibrating a pH electrode includes the further steps of taking a first pH reading with the pH electrode using a first pH buffer; taking a second pH reading with the pH electrode using a second pH buffer; and determining slope and offset values for the pH electrode.
- an ORP electrode there is provided an ORP electrode.
- the step of performing a titration analysis includes the step of performing a differential titration analysis.
- the step of determining the sensitivity of the ORP electrode There additionally provided the step of determining the sensitivity of the ORP electrode.
- the determination of an endpoint of the titration analysis includes the step of determining a turbid endpoint.
- This includes the use of a turbidity sensor to determine the turbid endpoint of the titration.
- this embodiment includes the further step of titrating a solution of unknown cyanide concentration, and may employ a silver ion.
- the use of a turbidity sensor to determine to turbid endpoint of the titration additionally may include the step of determining a change in the rate of change of turbidity of the chemical solution.
- a method of analysis of a chemical solution in a tank having a first chemical composition there are provided the steps of: -15- delivering a sample of the chemical solution having the first chemical composition to an analysis cell; performing an ion selective analysis on the chemical solution having the first chemical composition that has been delivered to the analysis cell, said step of performing the ion selective analysis including the further steps of: delivering a plurality of predetermined amounts of a standard solution having a known concentration of analyte to the chemical solution having the first chemical composition that has been delivered to the analysis cell; and measuring an electrode potential value of an ion selective electrode responsive to a predetermined chemical characteristic of the chemical solution having the first chemical composition that has been delivered to the analysis cell after delivering each of the predetermined amounts of the standard solution; determining a quantity of an analyte in the chemical solution having the first chemical composition that has been delivered to the analysis cell, said step of determining a quantity of an analyte
- the further step of predetermining the amounts of the standard solution having the known concentrations of analyte whereby the in the step of measuring an electro potential value of an ion selective electrode responsive to a predetermined chemical characteristic of the chemical solution having the first chemical composition that has been delivered to analysis cell after delivering each of the predetermined amounts of the standard solution, the electrode potential differences between successive ones of the measurements is approximately between 5 mV and 40 -16- mV.
- the electrode potential differences are approximately between 5 mV and 30 mV and the potential differences most preferably are approximately 20 mV.
- the step of extrapolating includes the step of extrapolating a plurality of the measured electro potential values back to the point of zero analyte concentration.
- the step of delivering the plurality of predetermined amounts of the standard solution having a known concentration of analyte, the concentration of the analyte in the standard solution is high relative to the concentration of the analyte in the chemical solution having the first chemical composition. This reduces the likelihood of diluting the chemical solution having the first chemical composition.
- Fig. 1 is a plan representation of coupling arrangement that is useful in the practice of the invention
- Fig. 2 is a simplified schematic representation of an analyzer arrangement that draws samples from a plurality of chemical tanks;
- Fig. 3 is a simplified schematic representation of an arrangement for combining a rinsing solvent with the purge gas arrangement of Fig. 2;
- Fig. 4 is a simplified schematic representation of an analyzer/controller embodiment of the invention, showing a control methodology
- Fig. 5 is a simplified schematic diagram of the fluid interconnections between various structural elements of the invention, on a first side of an installation panel;
- Fig. 6 is a simplified schematic diagram of certain additional fluid interconnections between various electrical components of the invention.
- Fig. 7 is a simplified schematic diagram of a nitrogen gas circuit, and further showing a stepper motor control board, on a second side of the installation panel shown in Fig. 5.
- an analyzer performs sensor differential tracking and alarming.
- the analysis uses a "differential" endpoint to avoid having to rely on an absolute or calibrated sensor value. When chemical equilibrium is reached during a titration, a large swing in the sensor reading occurs. This difference, or increased rate of change, is what is looked for in order to determine that a titration endpoint is reached.
- By tracking, reporting, and when necessary, alarming the sensor differential the user is alerted to potential problems and can elect to perform cleaning or preventative maintenance when necessary.
- the system of the present invention analyzes and filters data. Rather than merely accepting an analysis result as true, and then proceeding to employ the result for process control or feedback, a specific illustrative embodiment of the analyzer of the present invention repeats the analysis at least two more times to ensure that the value is repeatable. The result is then checked to determine whether its values are within predetermined ranges, thereby ensuring that the values are reasonable. If the value is repeatable and reasonable, it is accepted as having a high probability of being representative.
- the allowable difference among the trials is restricted to a predeterminable maximum, thereby permitting a selectable accuracy; and 3 the maximum number of trials is limited (usually to nine) so as to terminate unsuccessful attempts and warn the operator of present or impending equipment malfunction.
- This methodology both protects the process under control from spurious results as well as provides the user with an indication of the day-to-day performance of the - 18 - machine. An increased number of trials to reach a final result is a good warning that maintenance is required.
- an automated replenishment volume correction is based upon recipient tank liquid volume. Adjustment of the calculated batch amount advantageously is based upon the current tank level reading.
- Safety of the process is enhanced by the implementation of a replenishment volume safety limit
- the quantum of replenishment is limited irrespective of the amount indicated by the calculation.
- the analyzer/controller is stepped toward the target replenishment in several increments, particularly if the deviation of the result from the target is large.
- beaker rinsing and filling is effected by means of a high speed, low volume (consumption) spray.
- a spray rinse facilitates rapid cleaning and filling of the beaker while requiring only minimal water consumption. In most industries that perform chemical analysis, time and water are critical resources that need to be conserved.
- the stirring rate in the titration vessel of the chemical processing system is varied in accordance with established control parameters to achieve maximum mixing and maximum cleaning, while minimizing foaming and air entrapment.
- the variable stirring rate allows optimization of a variety of functions throughout the titration and cleaning procedure.
- the titration vessel is sealed, except for a vent/overflow tube that is routed to a drain via an overflow detector. The overflow detector thereby serves to detect and warn of malfunctions.
- the level in the titration vessel is monitored, or sensed, continuously, rather than by discrete point measurement technique.
- This enables a more accurate and continuously variable water and reagent delivery and for automated detection of malfunctions.
- Such problems may include, for example, insufficient reagents, low water pressure, and inoperative valves.
- continuous titration vessel level sensing it is possible to use simple, low cost valves to deliver and meter liquids into the titration vessel. While this is not of sufficient accuracy - 19 - for titrants (e.g. ⁇ 0.001 ml), it is sufficient for conditioning reagents or buffers (e.g., ⁇ 0.1 ml).
- Pneumatic level detection i.e., static liquid head pressure against a slowly bubbling immersed tube tip
- the sensing tube occupies only 0.125" outside diameter size and requires no "head space", / ' . e. , space for apparatus directly above the solution.
- the tube can be made of any semi-rigid or rigid material that is resistant to the solutions, such as Teflon or glass.
- Fig. 1 is a schematic representation of a coupling arrangement H) that is useful in the practice of the invention.
- the coupling arrangement uses a threaded element 1 1 to apply a compression load to a flared portion 13 of a tubing 14. As shown, the distal surface of flared portion 13 is urged sealingly against an elastomer washer seal 15, thereby effecting a connection. It is common in the industry today to use flared tube connections. In known arrangements, the end of a tube (not shown) is flared and literally squeezed between the tip of a threaded nut (not shown) and a hard mating surface (not shown) to create a leak-free connection.
- Fig. 2 is a simplified schematic representation of an analyzer 20 that illustrates a draw/purge sampling technique that is useful in the practice of the present invention. -20-
- Sample fluid provided to analyzers must, of course, be representative of the whole volume in the tank being sampled. To accomplish this samples sometimes are tapped off of a recirculating loop (not shown), usually in the form of a pressurized pipe containing flowing sample.
- the present analyzer accommodate this, and additionally can draw a sample from a static tank (not shown) several hundred feet away.
- samples are drawn from three tanks (not shown) via respective ones of valves 22, 23, and 24.
- the first objective here is to obtain a representative sample.
- Another objective is to accomplish this with the simplest, or least amount of, equipment.
- One known solution to this problem is to install a pump (not shown) at the tank and create a further recirculating loop (not shown).
- the analyzer of the present invention uses a relatively simple eductor 26 to create a vacuum and draw in sample whenever it is required across a sample detector 27.
- the unused portion of the sample is afterward blown back to the tank with pressurized air or nitrogen vis a valve 28 to purge the line and prepare for the next draw.
- a pump (not shown) can be used instead of the eductor to create a vacuum to conserve water, which still has the advantage of reduced maintenance requirement due to intermittent use only.
- an analyzer that is equipped to draw samples from several tanks can conserve cost and equipment complexity by utilizing a common vacuum system. Sample that reaches the vacuum system becomes waste. However, sample material that reaches the valves prior to the vacuum system does not become waste product.
- the above-described method of sampling also has the benefit of regularly back flushing sample filters (not shown) which may be installed in the sample lines. In conventional systems, sample material flows in only one direction through the filters, thereby causing premature fouling and clogging.
- the present inventive method of sampling also has the benefit of assuring that a fresh sample has arrived. Since the sample line is purged with gas after each analysis, -21- sample detector 27 may be used to confirm the transition from "sample absent" to "sample present.” This transition confirms the availability and presence of the sample and the proper operation of the sampling system. By comparison, a recirculating sample system may only have stagnant or unrepresentative sample in it, in which case the mere detection of sample presence is inadequate to ensure a correct analysis result.
- Fig. 3 is a simplified schematic representation that shows, in addition to purge gas valve 28 shown in Fig. 2, that a water or solvent rinse valve 29 can be added to clean the system between samplings of incompatible liquids, and to clean the purge gas valve itself.
- a water or solvent rinse valve 29 can be added to clean the system between samplings of incompatible liquids, and to clean the purge gas valve itself.
- This capability is important because dried sample can otherwise accumulate on this and other valves and cause them to fail.
- the arrangement of the rinse valve behind the purge gas valve is significant because without it that valve would be especially subject to sample accumulation.
- This air/water (or gas/solvent) combination is especially efficient at cleaning the apparatus with minimal time and solvent consumption, due the high propulsion and stream breakup caused by the gas.
- the gas causes what appears as a propelled rain within the tubes.
- the three tank sample valves (22, 23, and 24) shown in Fig. 2 can be replaced in certain embodiments of the invention with a single rotary valve (not shown) having multiple inlets and one outlet.
- This arrangement minimizes "dead legs" and in turn facilitates removal of old sample. This would be particularly advantageous when working with incompatible samples.
- rotary valves can wear easily, causing early valve failure, especially when rotated while full of sample. This vulnerability is overcome by the aforementioned gas/solvent rinse system (Fig. 3), whereby rotary valve rotations can be restricted to periods that the system is clean or empty.
- the analyzer of the present invention uses a variable sample volume device, which allows it to accommodate a wide range of sample concentrations and in turn be a more versatile tool by, for example, enabling it to run differing chemistries in series, each requiring a unique sample volume.
- the sampling device in the form of a syringe or burette, uses only the middle third of the sample column. This technique prevents both, air in the top third and sediment in the bottom third, from becoming part of the analyzed -22 - sample. This feature is facilitated by the present novel use of the variable volume sampling device.
- the vertical path remains filled with air until it is evacuated with a waste eductor or pump. This is important because trapped liquids can shift or delay titration endpoints.
- the flow of electrolyte is intermittent an controlled. All electrochemical sensors such as pH and ORP require a reference cell, a zero potential electrical connection to the solution. Many schemes have been tried for this, all of them with their benefits and disadvantages.
- a gel-filled reference cell electrolyte has been used. The electrolyte does not flow and in turn require refilling, but instead is stagnant. This cell electrolyte however will become poisoned and depleted due to ion migration in and out of the gel and drift over time, becoming non-zero in potential.
- a known alternative is a slowly flowing electrolyte reference. In this known arrangement, contaminants are flushed out and the zero-potential is maintained.
- the flow restricting device is in the form of a valve instead of a porous plug.
- the valve is located upstream, far from the sample. In this way it cannot clog or impede flow.
- the electrolyte flow is stagnant during measurements, thus improving stability, and it is allowed to flow briefly during the interval between measurements, thereby maintaining the zero potential junction.
- Another feature of the present invention is that the sample tube touches glass beaker wall. This breaks the droplets and allows an exact sample volume to be delivered.
- the titrant tube tips are aimed directly into the liquid vortex to minimize mixing time. Additionally, the titration vessel level sensing tube is cut at a 45 ° angle to minimize signal bounce as bubbles detach. -23 -
- Fig.4 is a simplified schematic representation of an analyzer/controller system 40, constructed in accordance with the principles of the invention, that is useful to illustrate a control methodology.
- an analyzer 41 which is integrated with a manager 42, receives a plurality of sample lines, specifically, a sample line 44 from an H 2 O 2 feed stock drum 48, a sample line 45 from a H 2 O 2 blend station 49, and a sample line 46 from an H 2 O 2 distribution tank 50.
- the figure additionally shows schematically replenishment controls 52, a local control unit 53 ("LCU 53"), and a level pressure transducer 55.
- the combination of analyzer 41 and manager 42 effect automatic analysis of a delivered sample under control of LCU 53.
- the results analysis are displayed, along with a parameter history, replenishment print-outs, system diagnostics, sensor calibration data, and operator alerts and alarms in a display 57.
- an alarm 59 is actuated, which incorporates a tower light and an audible signaling arrangement.
- a replenisher 60 is schematically indicated in this figure to include a precision syringe pump 62 for effecting automatic replenishment based on the results of the analysis.
- Replenishment controls 52 are used for multiple chemical delivery destinations from a common pump (not shown). Adjustment of the replenishment is performed under software control in accordance with a predetermined replenishment formula for adjustment that is based on the result of the analysis of H 2 O 2 replenishment feed stock drum 48.
- Level monitoring for distribution tank 50 includes hardware and software for monitoring the level of the distribution tank and adjusting the replenishment volume automatically, as calculated from the analysis.
- the level device at the distribution tank is in the form of a Teflon tubing 64 containing NO 2 at approximately between 2 and 10 psi. Distribution of the replenished liquid is effected, in this specific illustrative embodiment of the invention, via a schematically illustrated global supply loop 66, which may be pressurized.
- Fig. 5 is a simplified schematic diagram of the fluid interconnections between various structural elements of the invention.
- a reaction cell 80 which may be a glass beaker in the practice of the invention, contains a pair of chemical sensors 82 and -24-
- chemical sensor 82 is an ion selective electrode ("ISE") and chemical sensor 83 is a pH sensor or an ORP electrode.
- Reaction cell 80 is provided with a mixer 85 disposed thereunder.
- Deionized water is delivered to the reaction cell from a deionized water source 87 via a valve 88.
- Valve 88 is an electrically actuated, two-way valve. Delivery of precise quantities of a sample liquid and predetermined reagents is achieved by respective syringe assemblies 90, 91 , 92, and 93, which are, in this specific illustrative embodiment of the invention, dedicated to the sample, NaOH, Ag 2 NO 3 , and Na 2 S 2 O 3 , respectively.
- the syringe assemblies are controlled by stepper motors (not shown) that are controlled by the electronics shown in Fig. 7, via respectively associated ones of electric valves 95-
- FIG. 7 is a simplified schematic diagram of certain interconnections between various components of the invention. Elements of structure that previously have been discussed are similarly designated. As shown in this figure, electric valve 1 10 is connected to waste pump 1 12. Sample liquid from sampling chamber 155 is received via lines 1 16 and 117. Line
- a proximity sensor 1 18 which will issue a signal to a controller (not shown) that indicates that the sample has arrived.
- the sample then is drawn into syringe assembly 90 via 3 -way electrical valve 95.
- Fig. 6 further shows a sampling chamber 120 that is connected to a plurality of sample sources 121-125 via respectively associated ones of pneumatic valves 131-135.
- Each of the pneumatic valves is coupled to an air source 140 via a respectively associated one of electric valves 141-145.
- Figs. 5 and 6 show that deionized water from deionized water source 87 is conducted to the top of cell chamber 120 via electric valves 150 and 152.
- the bottom of cell chamber 120 is coupled to a common line 155 to which sample sources 121-125 -25- are coupled via the respectively associated ones of pneumatic valves 131-135.
- Common line 155 is coupled to a waste valve 160.
- the figures show a grab sample source 161 coupled via an electric valve 163 to common line 155, which as noted, is coupled to the bottom of cell chamber 120.
- Fig. 5 shows that in this specific illustrative embodiment of the invention, grab sample 161 is drawn from a trough 165.
- Fig. 6 illustrates that a KC1 electrolyte source 170 is disposed in reagent compartment 171.
- the KC1 electrolyte is supplied to the contents of reaction cell 80 via an electric valve 174.
- a KI source 176 and a H 2 SO 4 source 177 which also are located in the reagent compartment, are delivered to the reaction cell via respective ones of electric valves 178 and 179.
- the reagent compartment is also shown to contain a number of reagent sources that are supplied to respective ones of syringe assemblies 90, 91, 92, and 93. These reagents have previously been discussed.
- Electric valves 95-98 are 3-way valves that are controllable to permit the respectively associated syringe assemblies to take in a respective reagent, or to issue the precisely measured reagent to the reaction cell.
- Fig. 7 is a simplified schematic diagram of a nitrogen gas circuit, and further shows a stepper motor control board 180 and other electronic systems for developing electrode signals.
- a nitrogen source 184 supplies nitrogen to pressure regulators 182 and 183, each of which is connected to an associated one of pressure meters 185 and 186.
- Pressure regulated nitrogen is conducted from pressure regulator 183 via a line 188 to a T-coupler 190 that is interposed between electric valves 150 and 152. This nitrogen is available to purge sampling chamber 120.
- a further pressure regulated nitrogen is conducted via a valve 192 and a line 193 to reaction cell 80.
- signal conditioning amplifier 200 has an input voltage rating of ⁇ 2000 mV
- signal conditioning amplifier 201 has an input voltage rating of ⁇ 1000 mV
- signal conditioning amplifier 202 has an input voltage rating of 420 mV, with isolated ground.
- the stepper motors (not shown) that control the syringe -26- assemblies are themselves controlled via stepper motor control board 180.
- stepper motor control board 180 is capable of controlling four stepper motors.
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Automation & Control Theory (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Pathology (AREA)
- Clinical Laboratory Science (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- ing And Chemical Polishing (AREA)
- Control Of Non-Electrical Variables (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99916615A EP1068373A1 (en) | 1998-04-09 | 1999-04-09 | Automated chemical process control system |
JP2000543663A JP2002511613A (en) | 1998-04-09 | 1999-04-09 | Chemical process automatic control system |
AU34899/99A AU3489999A (en) | 1998-04-09 | 1999-04-09 | Automated chemical process control system |
KR1020007011146A KR20010072569A (en) | 1998-04-09 | 1999-04-09 | Automated chemical process control system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8124098P | 1998-04-09 | 1998-04-09 | |
US60/081,240 | 1998-04-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999053121A1 true WO1999053121A1 (en) | 1999-10-21 |
Family
ID=22162954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/007918 WO1999053121A1 (en) | 1998-04-09 | 1999-04-09 | Automated chemical process control system |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1068373A1 (en) |
JP (1) | JP2002511613A (en) |
KR (1) | KR20010072569A (en) |
AU (1) | AU3489999A (en) |
WO (1) | WO1999053121A1 (en) |
Cited By (9)
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FR2833365A1 (en) * | 2001-12-10 | 2003-06-13 | Air Liquide | PROCESS FOR REGULATING THE TITLE OF A SOLUTION, CONTROL DEVICE FOR THIS REGULATION AND SYSTEM INCLUDING SUCH A DEVICE |
FR2867696A1 (en) * | 2004-03-18 | 2005-09-23 | Air Liquide | Procedure for determining the concentration of a solution in different batches, e.g. for polishing semiconductors, uses pre-set formula based on individual volumes |
WO2006109144A1 (en) * | 2005-04-15 | 2006-10-19 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and apparatus for asynchronous blending and supply of chemical solutions |
ITTO20120621A1 (en) * | 2012-07-12 | 2014-01-13 | Sidel Spa Con Socio Unico | COLORIMETRIC METHOD AND DEVICE TO DETERMINE THE CONCENTRATION OF A PERACID AND / OR HYDROGEN PEROXIDE IN A SAMPLE SOLUTION |
US9835640B2 (en) | 2015-02-13 | 2017-12-05 | Abbott Laboratories | Automated storage modules for diagnostic analyzer liquids and related systems and methods |
US10739795B2 (en) | 2016-06-17 | 2020-08-11 | Air Liquide Electronics U.S. Lp | Deterministic feedback blender |
CN114527041A (en) * | 2020-10-30 | 2022-05-24 | 深圳市瑞图生物技术有限公司 | Display control method and device, sperm quality analysis system and storage medium |
CN115078744A (en) * | 2022-04-27 | 2022-09-20 | 广州伊创科技股份有限公司 | Control method, system, medium and product of industrial process on-line analyzer |
EP4166226A1 (en) * | 2012-11-13 | 2023-04-19 | Versum Materials US, LLC | Slurry supply and/or chemical blend supply apparatuses, processes, methods of use and methods of manufacture |
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US11906489B2 (en) * | 2020-03-02 | 2024-02-20 | Entech Instruments Inc. | Autosampler |
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Also Published As
Publication number | Publication date |
---|---|
AU3489999A (en) | 1999-11-01 |
EP1068373A1 (en) | 2001-01-17 |
KR20010072569A (en) | 2001-07-31 |
JP2002511613A (en) | 2002-04-16 |
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