AU593288B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU593288B2 – Process and apparatus for injecting a minute volume of a solution and an apparatus therefor
– Google Patents

AU593288B2 – Process and apparatus for injecting a minute volume of a solution and an apparatus therefor
– Google Patents
Process and apparatus for injecting a minute volume of a solution and an apparatus therefor

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Publication number
AU593288B2

AU593288B2
AU63819/86A
AU6381986A
AU593288B2
AU 593288 B2
AU593288 B2
AU 593288B2
AU 63819/86 A
AU63819/86 A
AU 63819/86A
AU 6381986 A
AU6381986 A
AU 6381986A
AU 593288 B2
AU593288 B2
AU 593288B2
Authority
AU
Australia
Prior art keywords
solution
injection
volume
nozzle device
nozzle
Prior art date
1985-10-15
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.)

Ceased

Application number
AU63819/86A
Other versions

AU6381986A
(en

Inventor
Hidechika Hayashi
Yuji Higo
Shuji Iwasaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Tosoh Corp

Original Assignee
Tosoh Corp
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.)
1985-10-15
Filing date
1986-10-10
Publication date
1990-02-08

1986-07-04
Priority claimed from JP15760886A
external-priority
patent/JPS62182665A/en

1986-10-10
Application filed by Tosoh Corp
filed
Critical
Tosoh Corp

1987-04-16
Publication of AU6381986A
publication
Critical
patent/AU6381986A/en

1990-02-08
Application granted
granted
Critical

1990-02-08
Publication of AU593288B2
publication
Critical
patent/AU593288B2/en

2006-10-10
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

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Classifications

G—PHYSICS

G01—MEASURING; TESTING

G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES

G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation

G01N30/02—Column chromatography

G01N30/04—Preparation or injection of sample to be analysed

G01N30/16—Injection

G01N30/20—Injection using a sampling valve

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

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T436/00—Chemistry: analytical and immunological testing

Y10T436/25—Chemistry: analytical and immunological testing including sample preparation

Y10T436/2575—Volumetric liquid transfer

Description

401
AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Form aO
(ORIGINAL)
FOR OFFICE USE 5932 88 Short Title: Int. Cl: Appli-ation Number: Lodged: 4 1 Iqk I cz, Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art:
CE
(CF
C.
44 1 41 4444t 4 44.4 To BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: TOYO SODA MANUFACTURING CO., LTD.
4560, OAZA TONDA
SHINNANYO-SHI
YAMAGUCHI-KEN
JAPAN
Actual Inventor: Address for Service: CLEMENT HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
*I Complete Specification for the invention entitled: PROCESS FOR INJECTING A MINUTE VOLUME OF A SOLUTION AND AN APPARATUS THEREFOR The following statement is a full description of this invention including the best method of performing it known to me:- Background of the Invention: Field of the Invention: The present invention relates to a process and an apparatus therefor for taking a minute volume of a solution from a reservoir and injecting the same solution into a vessel with high precision.
Description of the Prior Art: An injection apparatus for delivering minute volumes each ranging from several ya to several hundred U of a sample solution is generally used in biochemical immunoassay (IA) and liquid chromatography.
Previous injection apparatzsis usually provided with a cylinder device connected to the cavity of a nozzle device into which an object solution is sucked.
The solution is sucked by the backward motion of a piston of the cylinder device and injected by the forward motion of the piston. However, when this kind of an injection apparatus is used to inject minute volumes of a solution as mentioned above, significant errors of injection have often ei=met. oC -L.
Provided that the lower end of the nozzle in an inverted conical shape has a diameter of about 0.3 mm and the tube wall is about 0.3 0.5 mm thick, an injection error of several pt is inevitable when about 200 pt of a solution is sucked and injected by the forw ard and backward motion of a piston in the cylinder o evice. The error is not negligibly small when a high 61
LI©
3 injection precision is required. The error of course becomes more remarkable when a minute volume such as several pJ to several ten up is concerned.
Summary of the Invention: The present invention has been made to overcome above-mentioned problems and intends as this object to provide a process for injecting a minute volume of solution with a far improved injection precision and an apparatus for injection suitable to conducting the process.
Another object of this invention is to provide a process and an apparatus therefor which may be suitably employed in bioassay systems to pipet and deliver sample..
solutions.
H 4, According to the present invention there is provided a process for injecting a minute volume of a solution into a vessel with high precision, comprising the steps of: providing a reservoir including a nozzle device with a minute volume of a solution to be injected into a vessel;
V
using mechanical pressure acting on the volume to discharge the volume from said reservoir and inject the volume into said vessel via said nozzle device; and supplementing§ said discharge step by supplying a flow of pressurized air through said nozzle device during at least a final portion of said discharge step.
4 According to the present invention there is provided an apparatus for injecting a minute volume of a solution into a vessel with high precision, comprising: a nozzle device; a variable volume cylinder means fluidically connected to said nozzle device for filling and discharging a solution in and from said nozzle device; and means for supplementing said cylinder means during discharging of the solution, said supplementing means comprising means for selectively supplying a flow of compressed air through said nozzle device.
Detailed Description of the Invention: According to the inventors’ investigation, the ‘tt above mentioned injection error comes about due to the loss of the object solution to be delivered. Particularly, a part of the solution flows around to the outer wall of the C’t T nozzle or remains on the inner wall of the nozzle and is *r t left there undelivered. This probably has occurred mainly bfecause the speed of injection is lower in the final (also it i)i the initial) period of injection than in the midway of injection, if the injection results from the positive pressure applied from the cylinder device. This phenomenon becomes remarkable when a sample solution wets the nozzle material as solutions of .biological samples do and also when the piston of the 9 cylinder devici- is driven by the screw-driven mechanism using a pulse motor for delivering minute volumes. This is
L
Yr~drrPII»–«»- 4A explained, for example, by referring to Figs. and Fig. 6(a) shows the speed of a piston when the cylinder device is driven in the rectangular mode with a pulse motor, while Fig. 7(a) shows speed in the trapezoid mode with a pulse motor. The speed of injection from r L C t t t t tl g 4 t *4 4 t *4
L
^S 4 4 S* .^WW 4 o,
NQ
I!
tIA,, S, 17I pressure from a cylinder device and is applied without 1 1 1 r I rr.a i 1 ~r 17a pressure from a cylinder device and is applied without the nozzle, as shown in Fig. 6(b) and Fig. forms gradual slope in the final (also in the initial) period of injection.
In this connection, the present invention has 1cu-idd a r- el;ai air pressure applying operation in injecting a solution from the nozzle for tha purpose of minimizing the volume of the solution which may remain undelivered at the lower end of the nozzle. The air pressure applying operation is employed at least in the final period of injection, particularly to improve the A d.\ 4 8 *9 9
A,
A, 9 4 9* o 9P 9 *949 999rr 9 completeness in adding drops or solution. rig. 4tal (c) illustrate the case when the air pressure applying operation is adopted in the final period of injection and, in Fig. 5(a) the air pressure applying operation is adopted in both final and initial periods of injection.
The two figures demonstrate that a high injection speed can be obtained in the final period of injection.
The cylinder device is preferably employed to suck a solution in the nozzle and may be used in parallel) if there is no objection for injecting the solution.
The air pressure applying operation should be employed in the final period of injection (in parallel to use of the cylinder device, if required). However, in the intermediate period of injection, either the air pressure applying operation or the cylinder operation may be selected for use, or otherwise the two operations may be operated in parallel or alternated. Very high precision injection can be obtained by employing the cylinder 6-
-I
6 operation throughout the whole period of injection and the air pressure applying operation in parallel in the initial and final periods of injection.
In the preferred embodiment of this invention, the valve device is opened only for a short time after the initiation of the cylinder operation in the initial period of injection, to assure rapid growth of the speed with which the solution in the nozzle is delivered. Then the injection of the solution in the nozzle is continued by the cylinder operation and, in the final period, the valve device is opened again to assure the air pressure for rapid delivery of solution and the complete removal 4 e of the last drop from the lower tip of the nozzle.
The air pressure applying operation in the final period, as described above, should, preferably, continue in ordinary cases for 0.2 1 sec, more preferably, 0.2 0.5 sec, and the same in the initial period preferably for 0.1 0.2 sec.
The nozzle devices to which the present intoor 099. 0: vention can be applied include vertically movable nozzles S o as well as stationary nozzles. There is no restriction on the structure of nozzle device, but the device is generally used with a replaceable nozzle tip attached at the lowest end of the nozzle. a The cylinder device which is connected to cavity in the nozzle device and is mostly employed for sucking a solution may include those of the mechanical c ype in whichjpiston is moved by a screw driven mechanism 7
‘I
operated by a pulse motor and those operable by air pressure. A certain amount of a solution is sucked by the backward movement of the piston from the initial position to generate negative pressure in the cylinder connected to the nozzle, The piston is moved to the initial position during or after the injection of solution.
The compressed air source which is connected for the air pressure applying operation to the nozzle device and the valve device installed en route on the connecting line, are usually formed as an accumulator for the air pressure, a pump or a compressed air tank, and an electromagnetic valve of the ordinarily closed type.
Preferably a flow rate adjusting valve is inserted as part 1’ of the valve device on the connecting line. On-off of the S valves including the electromagnetic valve may be l accomplished by a manual switch, but on an automated apparatus the operation can be performed with the aid of a sequential control circuit which works in synchronisation with other devices for the injection.
S The air pressure applying operation for injection is conducted for the purpose of applying an air pressure large enough to allow as little solution as possible to n .remain on the inner and outer surfaces of lower end of the nozzle. The pressure should amount generally to 0.1 preferably 0.1 0.5 atmosphere by gauge. Too small an air I pressure is not sufficient to eliminate the remaining solution, but on the other hand too large a pressure may cause the solution from the lower end of the nozzle to be pattered.
i 0 O ‘3 ;w ‘ir I ih -8 The air flow rate is adjusted by an air flow adjusting valve to a range 20 to 100 mk/min, preferably to 60 mP/min.
The time duration in which the valve device is momentarily opened to apply an air pressure may be at the an amount of air sufficient to increase the solution ejection speed up to a prescribed rate in a short time, but not long enough to supply an amount of solution larger than the amount of solution contained in the nozzle. At the final period, the air pressure necessary for the last per:iod of ejection of solution is assured, and thus the amount of remaining solution can be minimized, and an r’ cc almost constant amount of the solution injection can be S assured from the initial period through the final period.
:In case the compressed air source employed is of such a kind as to generate a pressure only when required, the valve device may be composed of a check valve (a single f direction valve).
The present invention will be described in detail with reference to the accompanying drawings.
Brief Explanation of the Drawings: Fig. 1 through Fig. 3 show examples of embodiments of this invention.
Figs. 4 and 5 illustrate the speed of injection of solution according to this invention, while Figs. 6 and 7 show how the speed of injection varies when the process r¥ ^s carried out with single cylinder operation. t 1 -9- Detailed Description of the Preferred Embodiments: In Fig. 1, 1 is a nozzle tip which is replaceable and fitted to a nozzle holder 2, and the replacement is made by a replacing device not shown in the figure. A flow route is provided via the nozzle holder 2 connecting the axial hole in the nozzle tip 1 with an air tube 3, The air tube 3, at the end opposite that connected to the nozzle holder 2 is branched and one branch is connected to a cylinder volume 5 in a cylinder device 4 which is screw driven by a pulse motor 6, while the other branch is connected to an air pressure accumulator not o, shown in the figure via a valve device 9 which is composed of an ordinarily closed electromagnetic valve 7 and a flow *o rate adjusting valve 8. The electromagnetic valve 7 is connected to a control circuit not shown in the figure and is motivated, when required during the injection to temporarily open the route in synchronisation with the operation of other devices.
*Operations take place as follows.
At first, the nozzle tip 1 is fitted to the nozzle holder 2 and the lower end is dipped to a certain depth in a sample solution placed in the sample vessel.
Under the situation mentioned, the piston in the cylinder V device 4 is moved in the pull direction (downwards in the figure) to suck the sample solution in the nozzle tip 1. t The amount of sample taken can be controlled with a sufficiently high precision by controlling the distance of movement of the piston. It is also possible in the present embodiment to perform injection of a diluted solution. For :F .4 i 10 this purpose, a quantity of dilution water is first sucked in the nozzle tip, followed by suction of a sample solution.
Subsequently, the nozzle tip is pulled out of the sample vessel with the piston in the cylinder device being fixed and is brought just above a sample injection vessel.
Then the solution in the nozzle tip 1 is transferred by injection into the vessel. This is performed, for example, by moving the piston in the cylinder device in the «insert» direction or to the home position and the electromagnetic valve 7 is momentarily switched to the «open» state at the same time in order to «e momentarily apply a flow of compressed air at a rate determined by the flow rate adjusting valve 8. When the 0o injection has been finished, the electromagnetic valve 7 is S. momentarily switched to the «open» state to minimize the amount of solution remaining on the surface of the tip.
Thus, a course of injection is completed. The operations may be repeated for a further procedure.
Using the apparatus shown in Fig. 1, injections a 0 T RA 1- O 1 1 v I; 1 1 of a solution from the nozzle tip I were performed accordi.ng to the conditions and procedures described below.
y recision of Kinjection are} shown in CV-values in Table 1.
Comparison example: Injection of solution by the cylinder operation alone.
Example 1: Injection of solution by the cylinder operation, successively followed by the air pressure applying operation (operation in accordance with Fig. 4).
Example 2: Injection of solution by the successive operations of the temporary air pressure o applying operation, the cylinder operation and the air pressure applying operation (operation in accordance with Fig. Diameter of nozzle tip (at the lower end): 0.3 num Thickness of wall of nozzle tip: 0.3 0.5 nun 0 0Sample: 8 BSA in Saline Amount of injection (sucked and injected): See Table 1.
0 Amount of injection (Sample Dilution): 200 pt Operations of injection Cylinder operation: 200 pX/2 sec Pressure of air :0.1 atmosphere by gauge Duration of pressure application Example 1 (final period) 0.5 sec Example 2 (initial period) 0.1 sec (final period) :0.5 sec Flow rate, adjustment: 10 m2./l0 sec >1
I-
l2z Table 1 Amount of Comparison Examrple I Example 2 injection example Wk) CV (value) CV (value) CV (value) 100 1.88 1.60 0.35 1.53 1.85 0.22 5.29 0.85 0.97 3.13 1.05 0.96 6.05 0.86 0.78 .9′ 6.9 .9
S
.9 *5 .9 .9.
.9 4 .9 .9~ 5 .9 .9.9.9.9 in the table, CV (value) where n: frequency xF: mean of x xi x) x100 (10 for each example) .Is .9.9.9.9 .9 .9.9 .9 .9 .9.9 6* .9 .9 .9.9 a 5.9.944.9 .9 .9 .9 .9.9.9.94.9 .9 .9 .9 .9.9 .9 .9 .9.9 The result manifests the superiority of the precision in injection as obtained by the present invention to those in the comparison example. This invention can be expected to co)itribute, to those analytical systems in which precision in injection seriously influences analytical results, Particularly in Example 2 where the pressure application in the initia! period of injection accelerates the injection up to a certain speed from the start of the process, the solution to be injected does not flo~w around 13 to the outer wall of the nozzle. When a viscous solution is involved, the solution flows more slowly in the nozzle.
This solution is slowly injected by the pressure of the cylinder and the acceleration by the air pressure in the final period can effect complete injection of solution without leaving a significant trace at the lower end of the nozzle.
Of course, the present invention can be realized in various modified forms not restricted to the embodiment indicated in Fig. 1.
An example in Fig. 2, for instance, employs a bellows type air pump 10 as a compressed air source and a S check valve 11 in place of a valve device, other elements 9 S, being the same as in Example 1.
In case of this example, the air pressure is t generated by the mechanical or manual operation of the cylinder device to compress air in the air pump 8 and the pressure is transferred via the check valve 11 to the interior of the nozzle tip. This offers an economical construction of the apparatus because the compressed air source and the valve device can be obtained cheaply. The
S
S check valve should have so high a set pressure as not to be opened at the suction of solution and may be determined in correlation to the cylinder device.
The example shown in Fig. 3 employs a compressor (not shown in the figure) and a pressure regulator 12 as a compressed air source. Other components in the assembly are the same as in Fig. 1 except the electromagnetic valve
CI
I 14 7′ which is normally open. This example is evaluated to be advantageous because the compressed air from the compressed air source is normally rel’eased via the electromagnetic valve 7′ into the atmosphere instead of to the cylinder device.
When the injection apparatus of this example is employed in an analytical measurement system, the compressor can be also used for an energy source for other instruments. This permits increased freedom in designing the system and the common use of an apparatus.
As has been described above, the present invention enables the injecting of minute volumes of •e R solution to remarkably decrease the injection error due to a small fraction of the solution remaining at the lower end Sof the nozzle and therefore this invention can be applied to advantage to those apparatusus for analyses and measurements which require strict precision in njection.
In case a cylinder device prepared for suction of a solution is used for injection with an intention to realize complete delivery of the last drop of the solution, the stroke of the piston on injection is usually longer than the stroke on suction and therefore there is a void stoke on suction. Nowadays air cylinder devices employ smaller diameters and longer stems for the sake of more pr~c~a-sion. The trend may probably give rise to troubles in A controlling the amount of suction and adjustment of the injection speed. On the K~r. ‘Iu
-J
r k 2 4 15 contrary the apparatus of this invention is free from such a trouble and permits a small and precise injection to be realized with a large effect.
.4 4. 4 4 *4*44* 4~ 4 *4 4, *t 4. 4 4.
4 1 .4*4 I. p4 4 4 *44 .4 4 *4 0 4 9044554 4 4 44-4 4 4 4 .455444 4

Claims (1)

16- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A process for injecting a minute volume of a solution into a vessel with high precision, comprising the steps f providing a reservoir including a nozzle device with a minute volume of a solution to be-injected into a vessel; using mechanical pressure acting on the volume to discharge the volume from said reservoir and inject the volume into said vessel via said nozzle device; and supplementing said discharge step by supplying a S flow of pressurized air through said nozzle device during 4,1 at least a final portion of said discharge step. 2. An apparatus for injecting a mir.ate volume of a •t solution into a vessel with high precision, comprising: a nozzle device; a variable volume cylinder means fluidically 6 t connected to said nozzle device for filling and discharging a solution in and from said nozzle device; and ,r means for supplementing said cylinder means during discharging of the solution, said supplementing i means comprising means for selectively supplying a flow of compressed air through said nozzle device. 3. Process for injecting a minute volume of a I solution according to Claim 1, wherein said pressurized air is supplied in initial and final portions of said discharge tep and said mechanical pressure comprises positive Tl 0 17 a, pressure from a cylinder device and is applied without intermission through an intermediate period between the initial and final portions. 4. Apparatus for injecting a minute volume of a solution according to Claim 2, wherein the nozzle device is attached to a replaceable disposable-tip. DATED THIS 6TH DAY OF NOVEMBER, 1989 TOSOH CORPORATION By Its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. t t a a l

AU63819/86A
1985-10-15
1986-10-10
Process and apparatus for injecting a minute volume of a solution and an apparatus therefor

Ceased

AU593288B2
(en)

Applications Claiming Priority (4)

Application Number
Priority Date
Filing Date
Title

JP60-229699

1985-10-15

JP22969985

1985-10-15

JP61-157608

1986-07-04

JP15760886A

JPS62182665A
(en)

1985-10-15
1986-07-04
Method and apparatus for distributing minute amount of liquid

Publications (2)

Publication Number
Publication Date

AU6381986A

AU6381986A
(en)

1987-04-16

AU593288B2
true

AU593288B2
(en)

1990-02-08

Family
ID=26484999
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

AU63819/86A
Ceased

AU593288B2
(en)

1985-10-15
1986-10-10
Process and apparatus for injecting a minute volume of a solution and an apparatus therefor

Country Status (5)

Country
Link

US
(1)

US4810659A
(en)

EP
(1)

EP0219102B1
(en)

AU
(1)

AU593288B2
(en)

CA
(1)

CA1323004C
(en)

DE
(1)

DE3684863D1
(en)

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1987-05-02
1993-09-07
Teruaki Itoh
Apparatus for distributing sample liquid

JPH087222B2
(en)

1990-01-18
1996-01-29
持田製薬株式会社

Automatic dispensing dilution device

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(en)

1990-03-21
1998-01-16
Boehringer Ingelheim Int
Atomising devices and methods

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(en)

1990-07-05
1994-05-31
Hormec Technic Sa
Fluid dispenser, in particular for gluing parts

DE4092642C1
(en)

1990-07-10
1995-11-23
Musashi Engineering Inc
Improved constant viscous liq. delivery device

US5199607A
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1990-12-03
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Musashi Engineering, Inc.
Liquid dispensing apparatus

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1990-12-04
2000-11-15
Берінгер Інгельгайм Інтернаціональ Гмбх
Nozzle for delivery of the sprayed liquid stream, device for liquid spraying and device for regulation of liquid stream

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1990-12-04
1994-10-21
Dmw Tech Ltd
Atomising nozzles

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1991-04-24
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Toa Medical Electronics Co., Ltd.
Apparatus for diluting and mixing a liquid specimen

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1991-04-24
2000-02-28
シスメックス株式会社

Sample dilution mixing method and apparatus

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1991-05-09
1994-07-19
Alfred Berteloot
Electropneumatic apparatus for sampling rapidly predetermined volumes of a mixture, to be connected to a computer

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1991-09-18
1993-08-03
Ventana Medical Systems, Inc.
Liquid dispenser

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1991-11-15
1994-01-11
Burnett Lime Co., Inc.
Apparatus and method for dispensing a slurry

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(en)

1992-03-27
1993-10-14
Abbott Laboratories
Automated continuous and random access analytical system and components thereof

US7396512B2
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2003-11-04
2008-07-08
Drummond Scientific Company
Automatic precision non-contact open-loop fluid dispensing

US20070020579A1
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2005-07-25
2007-01-25
Michael Migdal
Tooth powdering device

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2005-11-29
2011-12-08
Leica Biosystems Nussloch Gmbh

tissue processor

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2010-12-17
2015-02-10
Burnett Lime Company, Inc.
Method and apparatus for water treatment

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2020-07-30
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Method and metering device for metered fluid delivery

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DEVICE FOR AUTOMATIC FEEDING OF SAMPLES TO AN ANALYSIS DEVICE

1986

1986-10-10
CA
CA000520333A
patent/CA1323004C/en
not_active
Expired – Fee Related

1986-10-10
AU
AU63819/86A
patent/AU593288B2/en
not_active
Ceased

1986-10-14
EP
EP86114225A
patent/EP0219102B1/en
not_active
Expired – Lifetime

1986-10-14
US
US06/918,726
patent/US4810659A/en
not_active
Expired – Lifetime

1986-10-14
DE
DE8686114225T
patent/DE3684863D1/en
not_active
Expired – Fee Related

Also Published As

Publication number
Publication date

US4810659A
(en)

1989-03-07

AU6381986A
(en)

1987-04-16

EP0219102A2
(en)

1987-04-22

EP0219102A3
(en)

1988-07-27

DE3684863D1
(en)

1992-05-21

EP0219102B1
(en)

1992-04-15

CA1323004C
(en)

1993-10-12

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