WO1993024825A1 - A method and system for sampling and determining the presence of contaminants in containers - Google Patents

A method and system for sampling and determining the presence of contaminants in containers Download PDF

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Publication number
WO1993024825A1
WO1993024825A1 PCT/US1993/004766 US9304766W WO9324825A1 WO 1993024825 A1 WO1993024825 A1 WO 1993024825A1 US 9304766 W US9304766 W US 9304766W WO 9324825 A1 WO9324825 A1 WO 9324825A1
Authority
WO
WIPO (PCT)
Prior art keywords
sample
container
volatiles
containers
beverage
Prior art date
Application number
PCT/US1993/004766
Other languages
English (en)
French (fr)
Inventor
Stephen J. Macdonald
Daniel B. Dennison
David H. Fine
David R. Rounbehler
Gregory J. Wendel
Original Assignee
The Coca-Cola Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Coca-Cola Company filed Critical The Coca-Cola Company
Priority to KR1019940704382A priority Critical patent/KR0184531B1/ko
Priority to JP6500619A priority patent/JPH07507393A/ja
Priority to AU43829/93A priority patent/AU672011B2/en
Priority to BR9306456A priority patent/BR9306456A/pt
Priority to EP93914003A priority patent/EP0646236A4/en
Publication of WO1993024825A1 publication Critical patent/WO1993024825A1/en
Priority to NO944597A priority patent/NO944597D0/no

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B07SEPARATING SOLIDS FROM SOLIDS; SORTING
    • B07CPOSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
    • B07C5/00Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
    • B07C5/34Sorting according to other particular properties
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/02Devices for withdrawing samples
    • G01N1/22Devices for withdrawing samples in the gaseous state
    • G01N1/2202Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G01N1/2214Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling by sorption
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/02Devices for withdrawing samples
    • G01N1/22Devices for withdrawing samples in the gaseous state
    • G01N1/24Suction devices
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76Chemiluminescence; Bioluminescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • G01N21/88Investigating the presence of flaws or contamination
    • G01N21/90Investigating the presence of flaws or contamination in a container or its contents
    • G01N21/9018Dirt detection in containers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0011Sample conditioning
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0078Testing material properties on manufactured objects
    • G01N33/0081Containers; Packages; Bottles
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/02Devices for withdrawing samples
    • G01N1/22Devices for withdrawing samples in the gaseous state
    • G01N1/2202Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/02Devices for withdrawing samples
    • G01N1/22Devices for withdrawing samples in the gaseous state
    • G01N1/2202Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G01N2001/222Other features
    • G01N2001/2223Other features aerosol sampling devices
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/02Devices for withdrawing samples
    • G01N1/22Devices for withdrawing samples in the gaseous state
    • G01N1/2226Sampling from a closed space, e.g. food package, head space
    • G01N2001/2229Headspace sampling, i.e. vapour over liquid

Definitions

  • the present invention relates to a container inspection system for sampling and determining the presence of certain substances, such as residues of contaminants within containers such as glass or plastic bottles. More specifically, the present invention relates to an improved sampling and analyzing system and method for determining the presence of residues of these contaminants in containers such as beverage bottles rapidly moving along a conveyor past a test station in a container sorting system.
  • Glass containers have the disadvantage of being fragile and, in larger volumes, of being relatively heavy. Accordingly, it is highly desirable to use plastic containers because they are less fragile and lighter than glass containers of the same volume.
  • plastic materials tend to absorb a variety of organic compounds which may later be desorbed into the product thereby potentially adversely affecting the quality of the product packed in the container. Examples of such organic compounds are nitrogen containing compounds such as ammonia, organic nitrogen compounds, and hydrocarbons including gasoline and various cleaning fluids.
  • specific substances e.g., contaminants such as nitrogen containing compounds and hydrocarbons
  • the objects of the present invention are fulfilled by providing a method of sampling and determining the presence of certain substances such as volatile residues in containers comprising the steps of: injecting fluid into said containers in order to displace at least a portion of the contents thereof; evacuating a sample of the container contents so displaced by applying suction thereto; and analyzing the sample evacuated to determine the presence or absence of the certain residues therein.
  • the fluid injected into the containers is compressed air which is injected through a nozzle to provide an air blast within the interior of the container. This air blast creates a cloud of the vaporous contents of the container which emerges from its opening whereby it may be evacuated by suction from outside of the container to sample a portion of the container contents.
  • Injection of fluid and evacuation of sample may be continuous operations or may be performed in steps. If steps are utilized, the step of initiating the injection of fluid into the container preferably precedes in time the initiation of the step of evacuating a sample in order to provide time for the formation of the sample cloud. However, the performance of the steps of injecting and evacuating may slightly overlap in time. Alternatively, the steps of injecting and evacuation may be spaced in time but this is dependent on the rate of sampling desired. A still further alternative is to synchronize the steps of injecting and evacuating to occur simultaneously for the same duration.
  • the injection of fluid from the nozzle and the suction applied by the evacuation means are continuously on at the test station.
  • the containers or bottles are rapidly and continuously moved through the test station on a rapidly moving conveyor.
  • the bottles are moved through the test station at a rate of 200 to 1000 bottles per minute.
  • a rate of 400 bottles per minute is preferable and is compatible with current beverage bottle filling speeds.
  • the desired test rate may vary with the size of the bottles being inspected and filled.
  • the injector nozzle is disposed upstream of the direction of conveyor movement from the suction tube of the evacuator so the injection of fluid into each container slightly precedes in time the evacuation of the resulting sample cloud.
  • a portion of the sample evacuated (about 90%) is diverted and the remaining portion of the sample passes to an analyzer for determination of the presence or absence of the certain residues.
  • the purpose of diverting the first portion of the sample is to limit the amount of sample that passes to the analyzer to manageable quantities in order to achieve high speed analysis.
  • the volume of the sample is too large it may foul or clog the detector.
  • the diverted portion of the first sample may be channeled through an optional air filter and recirculated into the compressed air being injected into subsequent containers to arrive at the test station. This provides for an efficient use of the diverted first portion of the sample and of a pump utilized for diversion and compression, and avoids the need to exhaust that first portion of the sample to the atmosphere surrounding the test site.
  • a wide range of contaminants are detectable without interference from product volatiles by providing a method of sampling and determining the presence of volatiles of certain contaminants in a container which was previously filled with a beverage, said container including an opening which is closeable by a cap, comprising the steps of: storing said container with the cap removed for a sufficient period of time to permit detectable quantities of volatiles of ingredients in residues of the beverages to evaporate and egress from said container; evacuating a sample of volatiles remaining in the container after expiration of said sufficient period of time; mixing the sample with a chemical reactant to cause a chemical reaction therewith in order to generate chemiluminescence of the reactants; and optically analyzing radiation emitted by chemiluminescence of the sample and reactant to determine the presence or absence of said volatiles of certain contaminants without interference from detectable levels of chemiluminescence of volatiles of ingredients of beverage residues.
  • Fig. 1 is a schematic block diagram of the sampling and residue analyzing system of the present invention illustrating a plurality of containers moving seriatim along a conveyor system through a test station, reject mechanism and washer station;
  • Fig. 2 is a block diagram illustrating a possible implementation of the system of Fig. 1 in a detector system in which the contaminant being detected may be a nitrogen containing compound;
  • Fig. 3 is a graph of signal intensity vs. wavelength of defected radiation emitted by chemiluminescence in the analyzer of the system of Fig. 2.
  • FIG. 1 there is illustrated a conveyor 10 moving in the direction of arrow A having a plurality of uncapped, open-topped spaced containers C (e.g. plastic beverage bottles of about 1500 c.c. volume) disposed thereon for movement seriatim through a test station 12, reject mechanism 28 and conveyor 32 to a washer system.
  • the contents of containers C would typically include air, volatiles of residues of contaminants, if any, and volatiles of any products such as beverages which had been in the containers.
  • An air injector 14 which is a source of compressed air is provided with a nozzle 16 spaced from but aligned with a container C at test station 12.
  • nozzle 16 is disposed outside of the containers and makes no contact therewith.
  • Nozzle 16 directs compressed air into containers C to displace at least a portion of the contents of the container to thereby emit a sample cloud 18 to a region outside of the container being tested.
  • the column of injected air through nozzle 16 into a container C would be typically of the order of about 10 c.c. for bottle speeds of about 200 to 1000 bottles per minute. A rate of 400 bottles per minute is preferable and is compatible with current beverage bottle filling speeds. The desired test rate may vary with the size of the bottles being inspected and filled. Only about 10 c.c. of the container contents would be displaced to regions outside of the bottle to form sample cloud 18.
  • an evacuator sampler 22 which may comprise a vacuum pump or the like coupled to a sampling tube or conduit 20.
  • the tube is mounted near, and preferably downstream (e.g., about 1/16 inch) of the air injector 14 so as to be in fluid communication with sample cloud 18 adjacent to the opening at the top of containers C.
  • Neither nozzle 16 nor tube 20 contacts the containers C at test station 12; rather both are spaced at positions outside of the containers in close proximity to the openings thereof. This is advantageous in that no physical coupling is required to the containers C, or insertion of probes into the containers, which would impede their rapid movement along conveyor 10 and thus slow down the sampling rate.
  • High speed sampling rates of from about 200 to 1000 bottles per minute are possible with the system and method of the present invention.
  • the conveyor 10 is preferably driven continuously to achieve these rates without stopping or slowing the bottles down at the test station.
  • a bypass line 24 is provided in communication with the evacuator sampler 22 so that a predetermined portion (preferably about 90%) of the sample from cloud 18 entering tube 20 can be diverted through bypass line 24.
  • the remaining sample portion passes to a residue analyzer 26, which determines whether specific substances are present, and then is exhausted.
  • One purpose of diverting a large portion of the sample from cloud 18 is to reduce the amount of sample passing from evacuator sampler 22 to residue analyzer 26 in order to achieve high speed analysis. This is done in order to provide manageable levels of samples to be tested by the residue analyzer 26.
  • Another purpose for diverting a portion of the sample is to be able to substantially remove all of sample cloud 18 by evacuator 22 from the test station area and divert the excess through bypass line 24.
  • the excess portion of the sample passing through bypass line 24 returned to air injector 14 for introduction into the subsequent containers moving along conveyor 10 through nozzle 16.
  • a microprocessor controller 34 is provided for controlling the operation of air injector 14, evacuator sampler 22, residue analyzer 26, a reject mechanism 28 and an optional fan 15.
  • Container sensor 17 including juxtaposed radiation source and photodetector is disposed opposite a reflector (not shown) across conveyor 10. Sensor 17 tells controller 34 when a container arrives at the test station and briefly interrupts the beam of radiation reflected to the photodetector.
  • Optional fan 15 is provided to generate an air blast towards sample cloud 18 and preferably in the direction of movement of containers C to assist in the removal of sample cloud 18 from the vicinity of test station 12 after each container C is sampled.
  • fan 15 is controlled by microprocessor 34 as indicated diagrammatically in Fig. 1.
  • fan 15 is continuously operating for the entire time the rest of the system is operating.
  • a reject mechanism 28 receives a reject signal from microprocessor controller 34 when residue analyzer 26 determines that a particular container C is contaminated with a residue of various undesirable types.
  • Reject mechanism 28 diverts contaminated rejected bottles to a conveyor 30 and allows passage of unconta inated, acceptable bottles to a washer (not shown) on a conveyor 32.
  • An alternative option is to place the bottle test station downstream of the bottle washer in the direction of conveyor travel, or to place an additional test station and sample and residue analyzing system after the washer. In fact it may be preferable to position the test station and system after the washer when inspecting bottles for some contaminants.
  • the contaminant is a hydrocarbon, such as gasoline which is insoluble in water
  • Certain hydrocarbons, on the other hand, not being water soluble, may then be sampled by a sampler 22 downstream of the washer, to the exclusion of the dissolved, water-soluble chemicals. Therefore, the detection of such hydrocarbons can be performed without potential interference from other water soluble chemicals if the bottles pass through a washer before testing.
  • a nozzle 16 is provided for generating an air blast which passes into a container (not shown) being inspected.
  • the air passing through nozzle 16 may be heated or unheated it being advantageous to heat the air for some applications.
  • Juxtaposed to the nozzle 16 is sample inlet tube 20 including a filter 40 at the output thereof for filtering out particles from the sample.
  • Suction is provided to tube 20 from the suction side of pump 82 connected through the residue analyzer 26. A portion of the sample (for example, 90-95% of a total sample flow of about 6000 c.c.
  • Blast control valve 50 receives control signals through line 50A from microprocessor controller 34 to normally maintain the valve open to permit the flow of air to the nozzle.
  • the detector assembly 27 in the embodiment of Fig. 2 is an analyzer which detects the residue of selected compounds such as nitrogen containing compounds in the containers being inspected by means of a method of chemiluminescence.
  • This type of detector is generally known and includes a chamber for mixing ozone with nitric oxide, or with other compounds which react with ozone, in order to allow them to react, a radiation-transmissive element (with appropriate filter) , and a radiation detector to detect chemiluminescence from the products of reaction.
  • characteristic light emission is given off at predetermined wavelengths such as wavelengths in the range of about 0.6 to 2.8 microns. Selected portions of the emitted radiation of chemiluminescence, and its intensity, can be detected by a photomultiplier tube.
  • nitrogen compounds such as ammonia
  • an oxidant e.g. oxygen in air
  • ambient air is drawn in through intake 60 and air filter 62 to an ozone generator 64.
  • Ozone is generated therein, as by electrical discharge into air, and is output through ozone filter 66 and flow control valve 68 to the detector assembly 27 wherein it is mixed with samples from containers input through intake tube 20, filter 40, flow restrictor 42, and converter 44.
  • the sample from intake tube 20 is passed through a converter 44, such as an electrically-heated nickel tube, in which the temperature is raised to approximately 800*C to 900"C before being input to detector assembly 27. Temperatures in the range of 400'C to 1400'C may also be acceptable.
  • NO nitric oxide
  • the nitric oxide is supplied to the chamber of the detector assembly 27.
  • Compounds other than NO which may react with 0 3 and chemiluminescence may also be produced in converter 44 e.g., organic compounds derived from heating of gasoline or cleaning residue.
  • a temperature controller 70 supplied with electrical power through a transformer 72 is used to control the temperature of converter 44.
  • the samples in the detector assembly 27 after passage through its chamber are output through an accumulator 85 and pump 82 to an ozone scrubber 56, and to an exhaust output 57 in order to clear the residue detector for the next sample from the next container moving along the conveyor 10 of Fig. 1.
  • an (optinal) fan may be employed to help clear any remaining sample cloud from near the sample inlet tube 20
  • Outputs from detector assembly 27 relating to the results of the tests are output through a preamp 84 to microprocessor 34 which feeds this information in an appropriate manner to a recorder 83.
  • the recorder 83 is preferably a conventional strip recorder, or the like, which displays signal amplitude vs. time of the sample being analyzed.
  • the microprocessor 34 may be programmed to recognize, as a "hit" or the detection of a specific residue, a signal peak from a photodetector of the detector assembly 27 which is present in a predetermined time interval (based on the sensed arrival of a container at the test station) and whose slope and amplitude reach predetermined magnitudes and thereafter maintain such levels for a prescribed duration.
  • the microprocessor controller 34 also has an output to a bottle ejector 28 to reject contaminated bottles and separate them from bottles en route to a washer.
  • a calibration terminal 86 is provided for residue analyzer 26 for adjusting the high voltage supply 26A associated with the detector assembly. Also provided is a recorder attenuator input terminal 88 connected to the microprocessor controller 34 for adjusting the operation of the recorder. Detector assembly 27 receives electrical power from the high voltage supply 26A.
  • Additional controls include operator panel 90 including a key pad and display section permitting an operator to control the operation of the detector assembly 27 in an appropriate fashion.
  • DC power is supplied to all appropriate components through DC power supply 78 coupled to the output of power supply PS.
  • An optional alarm enunciator 80A is provided for signaling an operator of the presence of a contaminated container.
  • Alarm enunciator 80A is coupled to the output of microprocessor controller 34 via output control line 80C.
  • a malfunction alarm 80B is also coupled to microprocessor controller 34 for receiving fault or malfunction signals such as from pressure switch 58 or vacuum switch 87 when pressures are outside of certain predetermined limits.
  • Other safety devices may be provided such as vacuum gauge 89, and back pressure control valve 54 for ensuring proper operation of the system.
  • Fig. 2 Most components of the entire system of Fig. 2 are preferably enclosed in a rust-proof, stainless steel cabinet
  • the cabinet is cooled by a counter-flow heat exchanger
  • the system of Fig. 2 in a preferred embodiment is utilized to detect the presence of nitrogen containing compounds in a sample, such as a refillable beverage bottle.
  • a sample such as a refillable beverage bottle.
  • Fig. 3 is a graph of signal intensity of radiation (in millivolts) vs. wavelength emitted by chemiluminescence
  • radiation emitted by chemiluminescence of nitrogen containing compounds is in the range of about 0.6 to 2.8 microns (near infrared to infrared radiation) . Consequently, when using the system of Fig. 2 and detector assembly 27 thereof, to look only for nitrogen containing compounds a cut-off filter 100 is utilized to block all chemiluminescent radiation of a sample of wavelengths below about 1 micron from reaching the photomultiplier detector of detector assembly 27.
  • the 1 micron cut-off filter 100 eliminates false reject signals which might be caused by high levels of "product” residue in a bottle under test. It is of course very important to eliminate, or minimize false reject signals to minimize, waste of refillable bottles.
  • samples in the lower part of column 1 include examples of beverage product tested ,and an indication of whether the bottles were capped, uncapped, and if uncapped the storage period of the residue-containing bottle with its top opening uncovered for example 15 hrs.
  • Capped means that the bottle was tested with a residue of the beverage procut present, and the top opening uncovered for only a brief period prior to testing.
  • Frresh means that the bottle was tested soon after opening it, and contained fresh product in liquid form, i.e. a substantially full bottle of beverage, rather than old fermented product.
  • the data in column 2 also indicates that for "uncapped” beverage bottles stored for 15 hrs. that "product” volatiles are undetectable (0 millivolts) by photomultiplier tube 104.
  • the discovery of the present invention that storage of beverage bottles in an uncapped state removes the possibility of developing false reject signals from "product' volatiles, is a most significant and beneficial discovery. That is, the process of the present invention which embodies the concept of storing uncapped beverage bottles for a sufficient time to permit "product" volatiles to dissipate, enables the detection of a wide range of other contaminants such as those listed in Table I in addition to contaminants including nitrogen containing compounds.
  • the materials to be inspected are not limited to substances in containers.
  • the method and system of the present invention could be used to detect volatiles adsorbed in shredded strips or flakes of resins, or plastic stock to be recycled for manufacturing new plastic beverage bottles.
  • This shredded or flaked plastic stock could be placed directly on a conveyor belt 10 and passed through test station 12 of Fig. 1; or the plastic stock could be placed in baskets, buckets or other types of containers disposed thereon and inspected in batches.
  • bottles being tested may be new bottles that have never been filled with a beverage.
  • new bottles could be tested for excessive acid aldehyde content, which may be a byproduct of the manufacturing process.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Engineering & Computer Science (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Measurement Of Radiation (AREA)
  • Automatic Analysis And Handling Materials Therefor (AREA)
PCT/US1993/004766 1992-06-01 1993-05-19 A method and system for sampling and determining the presence of contaminants in containers WO1993024825A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1019940704382A KR0184531B1 (ko) 1992-06-01 1993-05-19 용기중의 오염물질의 존재여부를 샘플링하고 결정하는 방법 및 시스템
JP6500619A JPH07507393A (ja) 1992-06-01 1993-05-19 容器の中の汚染物質をサンプリングしそしてその存在を決定する方法およびシステム
AU43829/93A AU672011B2 (en) 1992-06-01 1993-05-19 A method and system for sampling and determining the presence of contaminants in containers
BR9306456A BR9306456A (pt) 1992-06-01 1993-05-19 Processo de realizar a amostragem e determinar a presença de voláteis de determinados contaminantes em um recipiente que continha previamente uma bebida
EP93914003A EP0646236A4 (en) 1992-06-01 1993-05-19 METHOD AND SYSTEM FOR TAKING AND DETERMINING THE PRESENCE OF CONTAMINANTS IN CONTAINERS.
NO944597A NO944597D0 (no) 1992-06-01 1994-11-30 Fremgangsmåte og anordning for å ta stikkpröver og bestemme nærvær av forurensninger i beholdere

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US89086492A 1992-06-01 1992-06-01
US890,864 1992-06-01

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WO1993024825A1 true WO1993024825A1 (en) 1993-12-09

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PCT/US1993/004766 WO1993024825A1 (en) 1992-06-01 1993-05-19 A method and system for sampling and determining the presence of contaminants in containers

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JP (1) JPH07507393A (enrdf_load_html_response)
KR (1) KR0184531B1 (enrdf_load_html_response)
CN (1) CN1080723A (enrdf_load_html_response)
AR (1) AR248316A1 (enrdf_load_html_response)
AU (1) AU672011B2 (enrdf_load_html_response)
BR (1) BR9306456A (enrdf_load_html_response)
CA (1) CA2135878A1 (enrdf_load_html_response)
HU (1) HUT75420A (enrdf_load_html_response)
IL (1) IL105814A (enrdf_load_html_response)
MX (1) MX9303152A (enrdf_load_html_response)
NO (1) NO944597D0 (enrdf_load_html_response)
NZ (1) NZ253476A (enrdf_load_html_response)
RU (1) RU2125721C1 (enrdf_load_html_response)
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DE4427314A1 (de) * 1994-08-02 1996-02-15 Graessle Walter Gmbh Vorrichtung zur Untersuchung von Behältern auf Fremdgase
EP0752283A1 (de) * 1995-07-05 1997-01-08 Elpatronic Ag Verfahren und Vorrichtung zur Prüfung von Behältern

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Publication number Priority date Publication date Assignee Title
CN103675210A (zh) * 2013-12-12 2014-03-26 中国航空工业集团公司第六三一研究所 小型液冷快速接头污染度快速检测方法
RU170386U1 (ru) * 2016-04-22 2017-04-24 Федеральное государственное казенное военное образовательное учреждение высшего образования "Военная академия материально-технического обеспечения имени генерала армии А.В. Хрулёва" Министерства обороны Российской Федерации Устройство для определения содержания летучих веществ в продуктах питания
CN107991247A (zh) * 2017-12-08 2018-05-04 尹大路 一种食品检测装置及其检测方法
DE102018120693B4 (de) * 2018-08-24 2024-05-23 Joma-Polytec Gmbh Verfahren zur Reinigung von medienführenden Kunststoffbauteilen

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TR28391A (tr) 1996-05-23
NO944597L (no) 1994-11-30
KR0184531B1 (ko) 1999-05-15
KR950702028A (ko) 1995-05-17
NZ253476A (en) 1995-11-27
HUT75420A (en) 1997-05-28
JPH07507393A (ja) 1995-08-10
CN1080723A (zh) 1994-01-12
HU9403443D0 (en) 1995-02-28
BR9306456A (pt) 1998-06-30
CA2135878A1 (en) 1993-12-09
ZA933728B (en) 1994-03-01
NO944597D0 (no) 1994-11-30
TW227532B (enrdf_load_html_response) 1994-08-01
EP0646236A4 (en) 1996-02-28
AU672011B2 (en) 1996-09-19
IL105814A (en) 1997-07-13
IL105814A0 (en) 1993-09-22
RU2125721C1 (ru) 1999-01-27
MX9303152A (es) 1994-06-30
RU94046340A (ru) 1997-04-20
AU4382993A (en) 1993-12-30
AR248316A1 (es) 1995-07-12
EP0646236A1 (en) 1995-04-05

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