JPS6021443A - Automatic measurement of concentration of hydrofluoric acid of surface treatment liquid for food can made of aluminum - Google Patents
Automatic measurement of concentration of hydrofluoric acid of surface treatment liquid for food can made of aluminumInfo
- Publication number
- JPS6021443A JPS6021443A JP58129939A JP12993983A JPS6021443A JP S6021443 A JPS6021443 A JP S6021443A JP 58129939 A JP58129939 A JP 58129939A JP 12993983 A JP12993983 A JP 12993983A JP S6021443 A JPS6021443 A JP S6021443A
- Authority
- JP
- Japan
- Prior art keywords
- hydrofluoric acid
- concentration
- acid concentration
- sample
- standard solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
- G01N27/4165—Systems checking the operation of, or calibrating, the measuring apparatus for pH meters
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【発明の詳細な説明】
技術分野
この発明はフッ酸を含むアルミニウム食品鑵表面処理液
のフッ酸濃度の自動浦り′定装置に関する。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an apparatus for automatically measuring the concentration of hydrofluoric acid in a solution for treating the surface of aluminum food irons containing hydrofluoric acid.
従来技術
アルシ食品鑵ム食品罐の表面処理を行なうために、フッ
酸を含む酸性処理液が月いられている。この種の表面処
理工程においては、アルミニウム食品鑵を高速にかつ多
量に処理するので、表面処理液のフッ酸濃度を一定に維
持する必要上、測定を迅速に、かつ置頻度に行なうこと
が要求されるようになってきた。BACKGROUND OF THE INVENTION In order to perform surface treatment on aluminum food containers, an acidic treatment solution containing hydrofluoric acid is used. In this type of surface treatment process, aluminum food iron is treated at high speed and in large quantities, so it is necessary to maintain a constant hydrofluoric acid concentration in the surface treatment solution, which requires measurements to be carried out quickly and frequently. It has started to be done.
しかしながら、従来この種の表面処理液のフッ酸濃度の
自動測定装置は知られて2らず、人手による手動分析に
依存しており、甚だ非能率的であるとともに、その分析
作業工程は俵雑で尚連処理は出来なかった。However, there is no known automatic measuring device for the hydrofluoric acid concentration in surface treatment solutions of this type, and it relies on manual analysis, which is extremely inefficient and the analysis work process is cumbersome. So I couldn't process it.
上述の手動分析法は、フッ素イオン選択性電極と比較電
極(以下、電極と呼ぶ。)全使用した、ネルンストの理
論式に基づくイオン電極法でフッ酸a度金測定している
。In the above-mentioned manual analysis method, hydrofluoric acid a degree gold is measured by an ion electrode method based on Nernst's theoretical formula, which uses both a fluorine ion selective electrode and a reference electrode (hereinafter referred to as an electrode).
そして、処理工程の酸性処理液と同じ組成、濃度の下で
、フッ酸濃度の巻具なった既知の2種類の標準液を用い
て、′電極間に発生するフッ酸濃度に比例した電極電位
(以下、mV値と呼ぶ。)を測定し、片対数グラフ音用
いて、フッ酸濃度を片対数目盛、mV値を等分割同感に
した検量線を作成する。Then, under the same composition and concentration as the acidic treatment solution in the treatment process, using two known standard solutions with hydrofluoric acid concentrations, an electrode potential proportional to the hydrofluoric acid concentration generated between the electrodes was measured. (hereinafter referred to as mV value) is measured, and a calibration curve is created using a semi-logarithmic graph sound, with the hydrofluoric acid concentration on a semi-logarithmic scale and the mV value equally divided.
そのため、上述の検量線を用いて、試料のmV値からフ
ッ酸濃度をめるとき、フッfi1濃度が高くなるほど、
フッ酸濃度に対する片対数の目盛が詰1ってきて、かつ
粗くなってくるので、読み取りに個人差が生じ、精度が
悪く、なる。Therefore, when calculating the hydrofluoric acid concentration from the mV value of the sample using the above-mentioned calibration curve, the higher the hydrofluoric acid concentration, the more
The scale of the semi-logarithm for the hydrofluoric acid concentration becomes smaller and coarser, resulting in individual differences in reading and poor accuracy.
すなわち、処理工程のフッ酸濃度の管理粘度も悪くなる
とbう問題もめる。That is, there is a problem that the viscosity of controlling the hydrofluoric acid concentration in the treatment process also deteriorates.
発明の目的
この発明は上述の問題全解決するためになされたもので
ろって、フッ酸を含む表面処理取のフッ酸濃度全自動的
にかつ面精度で測定できる測定装Mを提供することを目
的とする。Purpose of the Invention The present invention has been made to solve all of the above-mentioned problems, and it is an object of the present invention to provide a measuring device M that can fully automatically measure the concentration of hydrofluoric acid in a surface treated sample containing hydrofluoric acid with surface accuracy. purpose.
発明の概要
この発明において、第1図に示すように、アルミニウム
食品鑵表面処理液と同じ組成、濃度の下でフッ酸濃度の
み異なった第1の標準液のフッ酸濃度CAと第2の標準
液のフッ酸濃度CBがマイクロ・コンピューターの記憶
部Mにppm (百方分率〕単位で記憶され、測定時に
は、第1の標1$液のフッ酸a度に比例する電圧EAと
第2の標準液のフッ酸濃度に比例する電圧EBと分析す
べぎ試料のフッ酸濃度に比例する電圧EXがマイクロ・
コンピューターへ読与込まれ、演算部Aモは、農ず、P
Pm単位のCA、CBがモル濃度の逆対数の単位(以下
、l) F単位と呼ぶ。)CAl、C84へより演算さ
れ、次に、分析すべき試料のPF小単位フッ酸濃度CX
が
より演算され、最後に、CXがPPm単位のCXへよ逆
演算され、CXがPPm値として表示される。Summary of the Invention In this invention, as shown in FIG. 1, the hydrofluoric acid concentration CA of the first standard solution and the second standard, which have the same composition and concentration as the aluminum food iron surface treatment solution but differ only in the hydrofluoric acid concentration, are The hydrofluoric acid concentration CB of the liquid is stored in the memory M of the microcomputer in units of ppm (100 parts), and at the time of measurement, the first standard voltage EA proportional to the degree of hydrofluoric acid a of the liquid and the second The voltage EB, which is proportional to the hydrofluoric acid concentration of the standard solution, and the voltage EX, which is proportional to the hydrofluoric acid concentration of the sample to be analyzed, are micro-
It is read into the computer, and the calculation section A is
CA and CB in the Pm unit are units of the antilogarithm of the molar concentration (hereinafter referred to as 1), which is called the F unit. )CAl, C84, and then the PF small unit hydrofluoric acid concentration CX of the sample to be analyzed.
is calculated, and finally, CX is inversely calculated to CX in PPm units, and CX is displayed as a PPm value.
制呻部Cは、第1の標準液と第2の標準液と試料とを自
動的にかつ順次交替的に一つの測定槽へ供給するように
、種々のバルブVの開閉の制御動作を行なう。The suppressor C controls the opening and closing of various valves V so that the first standard solution, the second standard solution, and the sample are automatically and sequentially alternately supplied to one measuring tank. .
本発明の実施例 第2図を診照して、本発明の詳細な説明する。Examples of the invention The present invention will be described in detail with reference to FIG.
lは、フッ酸を小量に含む酸性処理液の入っている糟で
ろる。槽1の酸性処理液はヌプレーボンプ2で導かれ、
多数のスプレーノズル(図示せず)からアルミニウム食
品鑵へ吹付けて表面処iMを行なう。ここに使用される
酸性処理膜は、日本ペイント社製「リドリン$12 O
A/#120EJの脱脂処理液に代表されるように、主
剤に硫酸、促進剤にフッ酸を含む水溶液である。1 is filtered in a pot containing an acidic processing solution containing a small amount of hydrofluoric acid. The acidic treatment liquid in tank 1 is led through Nuprey pump 2,
Surface treatment iM is performed by spraying onto the aluminum food pan from a number of spray nozzles (not shown). The acidic treatment membrane used here is “Ridrin $12 O” manufactured by Nippon Paint Co., Ltd.
As typified by the degreasing solution A/#120EJ, it is an aqueous solution containing sulfuric acid as a main ingredient and hydrofluoric acid as an accelerator.
フッ酸を小量に含む酸性処理液の試料C以下、測定液と
呼ぶ。)は、スグレーボンプ2の吐出側の配管3の途中
から分岐したチューブ4へ導く。Sample C, which is an acidic processing solution containing a small amount of hydrofluoric acid, is hereinafter referred to as the measurement solution. ) is led to a tube 4 branched from the middle of the piping 3 on the discharge side of the sougere pump 2.
そし−C、パルプ5を通過して測定槽6の底部から流入
し、測定槽6の上部からオーバーフローさせて排出する
。Then, it passes through the pulp 5, flows into the bottom of the measurement tank 6, overflows from the top of the measurement tank 6, and is discharged.
7は、測定槽6を洗浄するための洗浄水(例えば、純水
)を入れる貯槽でめる。洗浄水は、パルプ8を通過して
、自然流下で測定槽6へ供給される。7 is a storage tank containing cleaning water (for example, pure water) for cleaning the measurement tank 6. The washing water passes through the pulp 8 and is supplied to the measuring tank 6 under gravity flow.
9は、主剤の濃度を測定液の濃度と同じ既知の濃度、促
進剤のフッ眩渥友を測定液の濃度よりも低い既知の濃度
で調合した、第lの標準液Aの貯槽でめる。ここでは、
主剤に硫酸が主成分1−リドリン#1204Jの濃度を
1〔%〕、促進剤にフッ酸のぬ反を5(pprr+)に
調合した水溶欣を使用した。第1の標準液AfC、バル
ブlOを通過して、自然流下で測定槽6へ供給される。9 is prepared in a storage tank of the first standard solution A, in which the concentration of the base agent is prepared at a known concentration that is the same as the concentration of the measurement solution, and the concentration of the accelerator is prepared at a known concentration that is lower than the concentration of the measurement solution. . here,
An aqueous solution containing sulfuric acid as the main ingredient and a concentration of 1-ridorine #1204J as the main component of 1% and 5 (pprr+) of hydrofluoric acid as the accelerator was used. The first standard solution AfC passes through the valve IO and is supplied to the measurement tank 6 under gravity flow.
11は、主剤の濃度を測定液の濃度と同じ既知の濃度、
促進剤のフッ酸濃度盆測定液の濃度よシも尚い肌知の濃
度で調合(−た。第2の標準液Bの貯$j17である。11, the concentration of the base agent is a known concentration that is the same as the concentration of the measurement liquid;
The concentration of the accelerator hydrofluoric acid concentration basin measurement solution was also mixed at a known concentration (-).The second standard solution B was $17.
ここでは、主剤に仙℃酸が主成分の1−リドリン@ 1
20AJOL度全1〔%〕、促進剤にフッ酸のlJA度
を20 (ppm)に調合した水浴欣盆関用した。第2
の標4取りは、パルプ12を通過して、同然流下で測定
槽6へ供給される。Here, 1-ridrine@1 whose main ingredient is saccharic acid is used.
A water bath containing 20 AJOL (total 1%) and 20 (ppm) of 1 JA of hydrofluoric acid as an accelerator was used. Second
4 passes through the pulp 12 and is supplied to the measurement tank 6 in the same flow.
13は、測定槽6内の測定液、lたは洗浄水、または第
1の標準液Aを排出するためのパルプである。Reference numeral 13 denotes a pulp for discharging the measurement liquid, l or washing water, or first standard solution A in the measurement tank 6.
14ば、0e +’l+水全かくはんすることによって
泪u定槽6を洗浄したシ、第1の標準液Aや第2の標準
液Bに含葦れるフッ酸濃度を測定するときにかくはんし
たりするためのかくはん機でるる。14. The washing tank 6 was washed by completely stirring 0e + 'l + water, and it was stirred when measuring the concentration of hydrofluoric acid contained in the first standard solution A and the second standard solution B. There is a stirring machine for stirring.
測定槽6には、測定液、葦たは第1の標準液A、ぼたは
第2の標準液Bの中に含まれる遊離のフッ來イオン濃度
を測定するフッ素イオン選択性電極15、比較電極16
.温度補償電極17の3本の′電極が浸漬されている。The measurement tank 6 includes a fluorine ion selective electrode 15 for measuring the concentration of free fluorine ions contained in the measurement solution, the first standard solution A, and the second standard solution B, and a comparison electrode. electrode 16
.. Three 'electrodes of the temperature compensation electrode 17 are immersed.
測定液、または第1の標準液A、ぼたは第2の標準液B
の中の遊離のフッ累イオン濃度に比例する、フッ素イオ
ン選択性電極15と比較電極16間に発生する電極電位
18は、フッ紫イオンa度変換増幅器(以下、PF変換
増幅器と呼ぶ。) 19へ入力する。Measurement solution or first standard solution A, second standard solution B
The electrode potential 18 generated between the fluorine ion selective electrode 15 and the reference electrode 16, which is proportional to the free fluoride ion concentration in the fluorine ion a-degree conversion amplifier (hereinafter referred to as PF conversion amplifier) 19 Enter.
PF変換増幅器19は、電極電位18が高インピーダン
スの直流電位差信号であるために、これを低インピーダ
ンスへ変換するインピーダンス変換回路20と、アナロ
グ−デジタル変換器(以下、A−D変換器と呼ぶ。〕2
4へ入力するための信号レベルへ変換する信号変換凹路
21で構成される。Since the electrode potential 18 is a high impedance DC potential difference signal, the PF conversion amplifier 19 includes an impedance conversion circuit 20 that converts the electrode potential 18 into a low impedance signal, and an analog-to-digital converter (hereinafter referred to as an A-D converter). ]2
The signal converting concave path 21 converts the signal level into a signal level for input to 4.
また、PF変換増1陥器19には、特開昭56−119
781号に開示の如き方法で、サーミスタ等を用いた温
度補償電極17によって測定液、第1の標準液A、第2
の標準液Bの温度を検出して、温度変化に対する電極電
位18の変化をインピーダンス変換回路20の増幅度を
調節することによって自動補正する、自動温度補償回路
22を設けている。In addition, the PF conversion intensifier 19 has the following features:
By the method disclosed in No. 781, the measurement liquid, the first standard solution A, and the second standard solution are
An automatic temperature compensation circuit 22 is provided which detects the temperature of the standard solution B and automatically corrects changes in the electrode potential 18 due to temperature changes by adjusting the amplification degree of the impedance conversion circuit 20.
PF菱換増1陥器19の出力信号23は、A−D変換器
24へ入力する。The output signal 23 of the PF converter 19 is input to the AD converter 24 .
A−D変換器24は、アナログの出力信号23を2進化
符号のデジタル信号25へ変換し、そのデジタル信f
25 ’f:マイクロ・コンピューター26へ入力する
。The A-D converter 24 converts the analog output signal 23 into a binary code digital signal 25, and converts the analog output signal 23 into a binary coded digital signal 25.
25'f: Input to microcomputer 26.
マイクロ・コンピューター26は、制御、演算プログラ
ムの内容やそのプログラムに必要なパラメーターを記憶
する記憶装置(ROM+RAM)27と、制御、演算プ
ログラムの内容に基づいて制御、演算を実行するための
中央処理装置(CPU928と、さらに外部の機器との
信号の授受をする人力装置29や出力装置30で構成さ
れる。The microcomputer 26 includes a storage device (ROM+RAM) 27 that stores the contents of a control and calculation program and parameters necessary for the program, and a central processing unit that executes control and calculations based on the contents of the control and calculation program. (It is composed of a CPU 928, and a human power device 29 and an output device 30 that send and receive signals to and from external devices.
31は、マイクロ・コンピュータ26の制御、演算プロ
グラムに必要なパラメーターを設定するためのキー・ボ
ードである。キー・ボード31で設定したパラメーター
の設定数値は、エンコーダ32f:通してマイクロ・コ
ンピューター26へ記°1.αされる。31 is a keyboard for controlling the microcomputer 26 and setting parameters necessary for the calculation program. The set numerical values of the parameters set on the keyboard 31 are recorded to the microcomputer 26 through the encoder 32f.1. α is done.
マイクロ・コンピュータ26の第1出力信号33は、ド
ライバー34へ入力する。A first output signal 33 of the microcomputer 26 is input to a driver 34 .
ドライバー34には、パルプ5. 8. 10.12゜
13の開閉やかくはん機14の起動を操作する有接点リ
レー回路(図示せず)で構成され、これらの有接点リレ
ーの励磁や消磁は第1出力信号33によって制御される
。そして、パルプ5.8.10゜12.13の開閉状態
やかくはん機14の起動は、該当する有接点リレーの接
点の位置によって決まる。The driver 34 has pulp 5. 8. It is comprised of a contact relay circuit (not shown) that operates the opening/closing of the 10.12.degree. The opening/closing state of the pulp 5.8.10.degree. 12.13 and the activation of the agitator 14 are determined by the position of the contact of the corresponding contact relay.
マイクロ・コンピューター26の第2出力信号35は、
ドライバー36へ入力する。The second output signal 35 of the microcomputer 26 is
Input to driver 36.
ドライバー36には、電極15.16の異常を外部へ警
報するための有接点リレー(図示せず)を内蔵し、この
有接点リレーの励磁や消磁は第2出力信号35によって
制御される。そして、ドライバー36からは、有接点リ
レーの接点の位置状態を外部へ伝える警報信号37を発
し、この警報信号37を利用して、プゼー(図示せず)
を鳴らしたシ、表示灯(図示せず〕を点灯したシする。The driver 36 has a built-in contact relay (not shown) for warning the outside of abnormalities in the electrodes 15 and 16, and the excitation and demagnetization of this contact relay is controlled by the second output signal 35. Then, the driver 36 emits an alarm signal 37 that conveys the position state of the contact of the contact relay to the outside, and using this alarm signal 37, a
When the alarm beeps, an indicator light (not shown) is lit.
マイクロ・コンピューター26の第3出力信号38は、
デコーダ39全通して表示器40へ入力する。The third output signal 38 of the microcomputer 26 is
The entire decoder 39 is inputted to the display 40.
表示器40は、7セグメントの3桁の数字表示の発光ダ
イオード(LED)で構成され、測定液のフッ酸濃度を
百方分率単位(以下、PPm単位と呼ぶ。)でデジタル
表示する。The display 40 is composed of a seven-segment, three-digit light-emitting diode (LED), and digitally displays the hydrofluoric acid concentration of the measurement liquid in hundredth percent units (hereinafter referred to as PPm units).
マイクロ・コンピューター26の第4出力信号41ば、
デジタル−アナログ変換器(以下、D−A変換器と呼ぶ
。)42へ入力する。The fourth output signal 41 of the microcomputer 26,
It is input to a digital-to-analog converter (hereinafter referred to as a DA converter) 42.
D−A変換器42は、第4出力信号が2進化符号のデジ
タル信号であるため、これをアナログ信号へ変換し、さ
らに調節計や記録計などの機器が容易に接続できる信号
レベル、例えば、1〜5調節計44は、電位差計回路で
構成した設定器46と、有接点リレー47を動作させる
ための増幅回路45を有する。あらかじめ設定した設定
器46の管理するフッ酸濃度に対応した信号と、測定液
のフッ酸濃度に対応した出力信号43′f:比較し、正
の電位偏差が生じたときのみに増幅して有接点リレー4
7を励磁する。そして、この有接点リレー47の接点の
位置状態を外部へ伝える出力信号48を発する。Since the fourth output signal is a binary coded digital signal, the D-A converter 42 converts it into an analog signal, and also has a signal level that allows easy connection of devices such as a controller and a recorder, e.g. The 1 to 5 controllers 44 have a setting device 46 configured with a potentiometer circuit, and an amplifier circuit 45 for operating a contact relay 47. The signal corresponding to the hydrofluoric acid concentration managed by the preset setting device 46 and the output signal 43'f corresponding to the hydrofluoric acid concentration of the measurement solution are compared and amplified only when a positive potential deviation occurs. contact relay 4
7 is excited. Then, an output signal 48 that conveys the positional state of the contact of this contact relay 47 to the outside is generated.
なお、この調節計44に、P(比例動作)、P■(比例
積分動作)、PD(比例積分動作)、PID(比例積分
微分動作)の調節機能を有した調節計を採用してもよい
。Note that this controller 44 may be a controller having adjustment functions of P (proportional action), P■ (proportional integral action), PD (proportional integral action), and PID (proportional integral differential action). .
調節計44の出力信号48は、「リドリン#120A/
#120EJの脱脂処理液中のフッ酸濃度の下で、設定
器46によってろらかしめ設定したフッ酸a度から0.
1〜0.5 (ppm)の低下に相当する電位師差が生
じると、ポンプ操作部49全経てポンプ50全運転する
。The output signal 48 of the controller 44 is “Ridorin #120A/
Under the hydrofluoric acid concentration in the degreasing solution of #120EJ, the setting device 46 adjusts the hydrofluoric acid degree to 0.
When a potential difference corresponding to a decrease of 1 to 0.5 (ppm) occurs, the pump 50 is fully operated through the pump operating section 49.
ポンプ操作部49ば、ポンプ50の電wJ機を起動する
電磁スイッチ(図示せず〕を内ノにする。そして、この
電磁スイッチの開閉は、出力信号48によって操作され
る。The pump operation unit 49 turns on an electromagnetic switch (not shown) for starting the electric wjer of the pump 50. Opening and closing of this electromagnetic switch is operated by the output signal 48.
ポンプ50は、アルミニウム食品鑵の表面処理に使用す
る酸性処理液の、濃厚な促進剤のフッ酸を槽1へ補給す
る。The pump 50 replenishes the tank 1 with concentrated hydrofluoric acid, which is an acidic treatment solution used for surface treatment of aluminum food pans.
次に、マイクロ・コンピューター26の制御、演算プロ
グラムの内符を、第3図を参照して説明する。Next, the control of the microcomputer 26 and the internal code of the calculation program will be explained with reference to FIG.
キー・ボード31から、
■ 第1の標準液Aに含まれるフッ酸濃度CA(PPm
)
■ 第2の標準液Bに、含1れるフッ酸濃度CB(pp
m)
■ 第1の標準液Aの電極電位18の上限値EH(mV
)
■ 第1の標準液Aの電極電位18の下限値EL (m
V)
■ 第1の標準液Aと第2の標準液Bの電極電位18の
差、すなわち電位こう配
hs (rnV)
■ 洗浄水と第lの標準MA、第2の標準液Bの測定槽
6への供給時間、すなわち、パルプ8,10.12の開
時間 Tl(秒〕■ 測定槽6内の測定液、洗浄水、第
1の標準′Kf、Aの排出時間、すなわち、パルプ13
の開時間 T2〔秒〕
■ 測定槽6内の洗浄水による洗浄時間、すなわち、か
くはん機14の運転時間T3〔秒〕る。From the keyboard 31, ■ Hydrofluoric acid concentration CA (PPm
) ■ Hydrofluoric acid concentration CB (pp.
m) ■ Upper limit value EH of the electrode potential 18 of the first standard solution A (mV
) ■ Lower limit value EL of the electrode potential 18 of the first standard solution A (m
V) ■ Difference in electrode potential 18 between the first standard solution A and the second standard solution B, that is, potential gradient hs (rnV) ■ Measuring tank 6 for cleaning water, first standard MA, and second standard solution B supply time, that is, the opening time of pulps 8 and 10.
Opening time T2 [seconds] ■ Washing time with washing water in the measuring tank 6, that is, operation time of the agitator 14 T3 [seconds].
マイクロ・コンピューター26へ41[f51(手動操
作では、押ボタン・スイッチ(図示せず)の接点位置の
状態、または、自動操作では、有接点リレー(図示せず
)の接点位置の状態乃=パルス入力されて、ステップS
2でYESと判断されると、以下の校正動作を実施する
。(ステップS3)■ 表示器40は、校正信号51が
入力される直前の表示数値を保持する。41 [f51 (in manual operation, the state of the contact position of a pushbutton switch (not shown), or in automatic operation, the state of the contact position of a contact relay (not shown) = pulse) to the microcomputer 26 input, step S
If YES is determined in step 2, the following calibration operation is performed. (Step S3) ■ The display 40 holds the displayed numerical value immediately before the calibration signal 51 is input.
■ パルプ5を閉じて、測定槽6への測定液の供給全停
止する。■ Close the pulp 5 and completely stop supplying the measurement liquid to the measurement tank 6.
■ パルプ13全T2 (秒〕開いて、測定槽6内の測
定液を排出する。T2 (秒〕経過後、パルプ13を閉
じる。■ The pulp 13 is fully opened for T2 (seconds) to drain the measuring liquid in the measuring tank 6. After T2 (seconds) has elapsed, the pulp 13 is closed.
■ パルプ8.’tT、C秒〕開いて、測定槽6へ洗浄
水を供給する。−rl(秒〕経過後、バルブ8を閉じる
。■ Pulp8. 'tT, C seconds] is opened to supply cleaning water to the measuring tank 6. -rl (seconds), close the valve 8.
■ かくはん機14全T3〔秒〕運転して、洗浄水をか
くはんしながら測定槽6内を洗・浄する。T3〔秒〕経
過後、かくはん機14を停止する。■ Operate the stirrer 14 for a total of T3 [seconds] to wash and clean the inside of the measuring tank 6 while stirring the washing water. After T3 [seconds] has elapsed, the agitator 14 is stopped.
■ バルブ13をT2 [秒]開いて、測定槽6内の洗
浄水全排量する。T2〔秒〕経過後、バルブ13を閉じ
る。■ Open the valve 13 for T2 [seconds] and drain all the cleaning water in the measurement tank 6. After T2 (seconds) has elapsed, the valve 13 is closed.
■ バルブ8をT1〔秒〕開いて、測定槽6へ第1の標
準液Aを供給する。T1 (秒〕経過後、バルブ8を閉
じる。(2) Open the valve 8 for T1 [seconds] and supply the first standard solution A to the measurement tank 6. After T1 (seconds) has elapsed, valve 8 is closed.
■ かくはん機14を運転して、測定槽6内の第1の標
準液A全かくはんする。■ Operate the stirrer 14 to completely stir the first standard solution A in the measuring tank 6.
■ 第1の標準液Aの電極電位18 EA(mV)を7
111I是し、その値全読み込んで記°1.はする。■ Electrode potential of the first standard solution A 18 EA (mV) 7
111I, read all the values and write them down.1. I will.
[株] かくはん機14’に停止する。[Stocks] Stop at agitator 14'.
(Ll) EA(mV))SEH(mV、14たはE
A C111V 、1:>EL(mV)でるることを確
認する。(Ll) EA (mV)) SEH (mV, 14 or E
Confirm that A C111V, 1:>EL (mV) is obtained.
もし、EACmv〕が111記の条件に入らなければ、
第2出力信号35を発し、電極15゜16の異常の報知
をする。If EACmv] does not meet the conditions of Section 111,
A second output signal 35 is generated to notify abnormality of the electrodes 15 and 16.
■ バルブ13(c−T (秒〕開いて、測定槽6内の
第1の標準液Aを排出する。T2 (秒〕経過後、バル
ブ13を閉、じ′る。(2) Open the valve 13 (c-T (seconds) to discharge the first standard solution A from the measuring tank 6. After T2 (seconds) has elapsed, close the valve 13.
■ バルブ8’kTl(I秒〕開いて、測定槽6へ洗浄
水を供給する。T□〔秒〕経過後、ノクルプ8を閉じる
。■ Open the valve 8'kTl (I seconds) to supply cleaning water to the measuring tank 6. After T□ [seconds] has passed, close the noklup 8.
@ かくはん機14をT3〔秒〕運転して、洗浄水をか
くはんしながら測定槽6内全洗浄する。T 〔秒〕経過
後、かくはん機14を停止する。@ The agitator 14 is operated for T3 [seconds] to completely clean the inside of the measuring tank 6 while stirring the cleaning water. After T [seconds] have elapsed, the agitator 14 is stopped.
■ バルブ13をT2 C秒〕開いて、泪り定木曹6内
の洗浄水を排出する。T2〔秒〕経過後、バルブ13を
閉じる。■ Open the valve 13 for T2C seconds to drain the cleaning water in the Narimirisakiso 6. After T2 (seconds) has elapsed, the valve 13 is closed.
■ 7< )vブ12を11 〔秒〕開いて、泪U定(
曹6内へ第2の標準液15f供給する。Tl〔秒〕Ma
後、ノ<71/プ12を閉じる。■ 7 < ) Open the v 12 for 11 [seconds] and hold the tears (
15f of the second standard solution is supplied into the soda 6. Tl [seconds] Ma
After that, close No.71/P12.
Oかくはん機14を運転して、測定槽6内の第2の標準
液Bをかくはんする。The O stirrer 14 is operated to stir the second standard solution B in the measurement tank 6.
■ 第2の標準液Bの電極電位18EB(mV)を測定
し、その値を読み込んで記憶する。(2) Measure the electrode potential of 18EB (mV) of the second standard solution B, read and store the value.
■ かくはん磯14を停止する。■ Stop stirring iso 14.
QD EA(mV)−En(mV)≧E 5 (m V
、lでるることを確認する。QD EA (mV) - En (mV) ≧ E 5 (m V
, check that it appears.
もし、EA(mV、l−EB(mV)がitJ記の条件
に入らなければ、第2出力信号35を発し、’rljJ
M 15 、 16の異常の報知をする。If EA (mV, l-EB (mV) does not meet the conditions described in itJ, the second output signal 35 is generated and 'rljJ
Notifies abnormalities of M 15 and 16.
校正動作が終了すると、ステップS4に進みバルブ5を
開いて、測定槽6へ測定液を供給する。When the calibration operation is completed, the process proceeds to step S4, where the valve 5 is opened and the measurement liquid is supplied to the measurement tank 6.
そして、ステップS5で測定液の電極電位18Ex (
mV ) を泪U廻して、その値を逐次読み込さ、下記
の7演算式i、 fl、 III、 JYによって、測
定液中のフッ酸濃度をPPm単位で算出する。Then, in step S5, the electrode potential 18Ex (
mV), the values are sequentially read, and the hydrofluoric acid concentration in the measurement liquid is calculated in PPm using the following 7 calculation formulas i, fl, III, and JY.
■ マイクロ・コンピューター26の記憶装置27から
PPm単位の第1の標準液のフッ酸濃度すなわちCAC
PPm)を読出して、モル濃度の逆対数の単位(以下、
I’ F単位と呼ぶ。)、すなわち、C;A’(P F
)へ1式によって変換する。(ステップS6)
■ 次に記憶装置27からppm単位の第2の標準液の
フッ酸濃度すなわちcBCppm〕を読出して、PFF
単位すなわちCB’ (、P ’I; )へ■式によっ
て変換する。(ステップS7)
■ 測定液に含まれるフッ酸濃度をPI7単位、すなわ
ちCx’[PF)を]■式によって演算する。■ The hydrofluoric acid concentration of the first standard solution in PPm units, that is, the CAC, is stored in the storage device 27 of the microcomputer 26.
PPm) and the unit of the antilogarithm of the molar concentration (hereinafter referred to as
It is called IF unit. ), that is, C;A'(P F
) to be converted by equation 1. (Step S6) ■ Next, read the hydrofluoric acid concentration of the second standard solution in ppm from the storage device 27, that is, cBCppm], and
Convert to the unit CB' (, P'I; ) using the formula. (Step S7) ■ Calculate the concentration of hydrofluoric acid contained in the measurement liquid in PI7 units, that is, Cx'[PF] by the following formula.
(ステップS8)
■ CX′〔PF〕からppm単位、すなわちCX(p
pm)へIV式によって変換する。(ステップ59)
9000
CX−・・・・・・1v
e ’i< P (2,303X CX)以上の演算式
−x、m、m、IVによって算出した測定液に含互れる
PPm単位のフッ酸濃度に相当する2進化符号のデジタ
ル信号を、第3出力信号38と第4出力信号41とし表
示器40と調節計44へ供給して、槽1の酸性処理液に
含まれるフッ酸a度をPPm単位で表示するとともに、
槽1への濃厚なフッばの補給′ff:制御して、フッ酸
濃度を一定に管理する。(Step S8) ■ From CX'[PF] in ppm unit, that is, CX(p
pm) by the IV formula. (Step 59) 9000 CX-...1v e 'i < P (2,303 A digital signal with a binary code corresponding to the acid concentration is supplied as the third output signal 38 and the fourth output signal 41 to the display 40 and the controller 44, and the a degree of hydrofluoric acid contained in the acidic treatment liquid in the tank 1 is determined. is displayed in PPm, and
Replenishment of concentrated hydrofluoric acid to tank 1'ff: Controlled to keep the hydrofluoric acid concentration constant.
効果
以上説明したように、この発明は、アルミニウム食品鑵
の表面処理液の試料に浸漬した電極電位に基づいて、試
料のフッ酸#度がPPm値として自動的に演算、表示さ
れるので、従来のように検量線を作成することなく、フ
ッ酸a度を迅速に、かつ正確に知ることができ、しかも
、表面処理液のフッ酸a度の管理も迅速に行なうことが
できる。Effects As explained above, this invention automatically calculates and displays the hydrofluoric acid concentration of the sample as a PPm value based on the potential of the electrode immersed in the sample of the surface treatment solution for aluminum food iron. The hydrofluoric acid a degree can be quickly and accurately determined without creating a calibration curve as in the above method, and the hydrofluoric acid a degree of the surface treatment solution can also be quickly managed.
第1図は本発明の概略を示す回路図、第2図は本究明の
一笑施例を示すブロック図、第3図は第2図の装置の動
作を示すフローチャートである。
1・・・糟、 6・・・測定槽、15,16.17・・
・電極、5,8.10,12.13・・・バルブ、26
・・・マイクロ・コンピューター。
特許出願人 日本ペイント株式会社
代理人弁理士青山 葆外1名
第3図(0)
スター
を北
橡4斌Aのf度
Ca(typ笥)
標碑J練βの91度
Ca(pp乞ン
殻 之
rs (FIVン
穀 定
搾りA1医電位θ
EL 偏■ン
後足
ε
パルプLLO,rZ、n蒙
T1(什)玄帷定
羽トjχIy、i’+
いルフt3ryr轡qrm晴ノ
2抹
冴締杵廟
を蛋臣払−jAめ、If&−四)
手続補正書(自発)
]、事件の表示
昭和58年特許願第 12’9939 号2、発明の名
称
アルミニウム食品鑵表面処理液のフッ酸濃度の自動測定
装置
3補正をする者
4、代理人
および図面
7、補正の内容
(1)特許請求の範囲を別紙の通り訂正。
(2)明細書6頁2行「吐出側」とあるを1吐出側」に
訂正。
(3)同6頁14行〜15行「主成分「リドリン#12
0AJの」とあるを[主成分の[リドリン#120AJ
の1に訂正。
(4)同7頁1行「調合した。第2の」とあるを「調合
した、第2の」に訂正。
(5)同10頁17行「ブゼー」とあるを「ブザ゛−」
に訂正。
(6)同11@9行「第4出力信号が」とあるな「第4
出力信号41が」に訂正。
(7)同15頁10行および12行「バルブ8を」とあ
るを「バルブ10を」に訂正。
(8)同19頁2行「第4出力信号41とし表示器40
と」とあるを「第4出力信号41として、表示器40と
」に訂正。
(9)第1図、第3図(、)、第3図(b)、第3図(
(りを別紙のとおり訂正。
別紙
特許請求の範囲
(1)アルミニウム食品鑵表面処理液と同じ組成、濃度
の下で7ツ酸濃度のみ異なった第1の標準液の7ツ酸濃
度CΔと第2の標準液のフッ酸濃度cBとを1)l)I
fl (百方分率)単位で記憶する記憶手段と、第1の
標準液、第2.!2標準液、アルミニウム食品鑵表面処
理液の試料を一つの測定槽へ順次交替的に供給させる制
御手段と、上記一つの測定槽に設けられ、この測定槽へ
供給される第1の標準液、第2の標準液、試料の各液の
フン酸濃度を表わす電圧EΔ、EB :Ey、を出力す
る検出手段と、検出手段から得られた電圧EA 、EB
、EXと記憶手段に記憶されているC八、CBとから
試料のフッ酸濃度CXを演算する演算手段と、演算手段
から得られた濃度Cχをl)l)m単位で表示する表示
手段とからなることを特徴とするアルミニウム食品鑵表
面処理液の7ツ酸濃度の自動測定装置。
第1図FIG. 1 is a circuit diagram showing an outline of the present invention, FIG. 2 is a block diagram showing a simple embodiment of the present invention, and FIG. 3 is a flow chart showing the operation of the apparatus shown in FIG. 2. 1...Castle, 6...Measuring tank, 15,16.17...
・Electrode, 5, 8.10, 12.13...Valve, 26
...Microcomputer. Patent applicant: Nippon Paint Co., Ltd. Representative Patent Attorney Aoyama Sogai 1 Figure 3 (0) The star is Hokusai 4 Bin A's f degree Ca (typ 笥) Marker Jren β's 91 degree Ca (pp beg) Husk rs (FIVn Grain Fixed Squeezing A1 Medical Potential θ EL Partial Hind Leg ε Pulp LLO, rZ, n Mon T1 (什) 1981 Patent Application No. 12'9939 2 Title of Invention Automatic Acid Concentration Measuring Device 3 Person who makes the correction 4, agent and drawing 7 Contents of the amendment (1) The scope of the claims is corrected as shown in the attached sheet. (2) Line 2 of page 6 of the specification states “Discharge side” 1 discharge side.”
0AJ” [Main ingredient [Ridorine #120AJ
Corrected to 1. (4) On page 7, line 1, ``I mixed it. The second'' was corrected to ``I mixed it, the second.'' (5) On page 10, line 17, “Buzee” is replaced with “Buzze-”
Corrected. (6) Same line 11 @ 9th line ``4th output signal''.
Output signal 41 is corrected to ``. (7) On page 15, lines 10 and 12, "Valve 8" was corrected to "Valve 10." (8) Page 19, line 2 “4th output signal 41 and display 40
"and" was corrected to "as the fourth output signal 41 and the display 40." (9) Figure 1, Figure 3 (, ), Figure 3 (b), Figure 3 (
(Corrected as shown in the attached sheet. Attachment Claims (1) The 7-acid concentration CΔ and the The hydrofluoric acid concentration cB of the standard solution in 2 and 1) l) I
a storage means for storing information in units of fl (hundredth fractions); a first standard solution; a second standard solution; ! 2. A control means for sequentially and alternately supplying samples of the standard solution and aluminum food surface treatment solution to one measurement tank; a first standard solution provided in the one measurement tank and supplied to the measurement tank; A detection means for outputting voltages EΔ, EB:Ey, representing the hydronic acid concentration of the second standard solution and each sample solution, and voltages EA, EB obtained from the detection means.
, EX and C8 and CB stored in the storage means, a calculation means for calculating the hydrofluoric acid concentration CX of the sample, and a display means for displaying the concentration Cχ obtained from the calculation means in l) l) m units. An automatic measuring device for measuring the concentration of 7-acid in an aluminum food iron surface treatment solution. Figure 1
Claims (1)
!iの下でフッ酸濃度のみ異なった第1の標準液のフッ
酸濃度CAと第2の標準液のフッ酸濃度CBと’r:
ppm (百方分率)単位で記憶する記憶手段と、第1
の標準液、第2標準欣、アルミニウム獄品(1商表面処
理液の試料を一つの測定槽へ順次交81j勺に供給させ
る制御手段と、上記一つの測定槽に設けられ、この測定
槽へ供給される第1の標準1反、第2の標準液、試料の
容顔のフッm濃度を表わす電圧EA、l!、B、EXを
出力する検出手段と、検出手段から得られた電圧EA、
EB、EXと記憶手段に記゛LはされているCA、C1
0とから試料のフッ酸濃ことを特徴とするアルミニウム
食品鑵表面処理液のフッ酸濃度の自動測定装置。(1) Same composition as aluminum food surface treatment, a)
! The hydrofluoric acid concentration CA of the first standard solution and the hydrofluoric acid concentration CB of the second standard solution, which differ only in the hydrofluoric acid concentration under i, 'r:
a storage means for storing in units of ppm (percentage per hundred);
a control means for sequentially supplying the standard solution, the second standard sample, and the sample of the aluminum surface treatment solution to one measuring tank in an alternating manner; a detection means for outputting voltages EA, l!, B, and EX representing the fluorine concentration of the supplied first standard, second standard solution, and sample; and a voltage EA obtained from the detection means;
EB, EX and CA, C1 whose "L" is recorded in the storage means
An automatic measuring device for the hydrofluoric acid concentration of an aluminum food surface treatment solution, which is characterized in that the hydrofluoric acid concentration of the sample is from 0 to 0.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58129939A JPS6021443A (en) | 1983-07-15 | 1983-07-15 | Automatic measurement of concentration of hydrofluoric acid of surface treatment liquid for food can made of aluminum |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58129939A JPS6021443A (en) | 1983-07-15 | 1983-07-15 | Automatic measurement of concentration of hydrofluoric acid of surface treatment liquid for food can made of aluminum |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6021443A true JPS6021443A (en) | 1985-02-02 |
Family
ID=15022166
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58129939A Pending JPS6021443A (en) | 1983-07-15 | 1983-07-15 | Automatic measurement of concentration of hydrofluoric acid of surface treatment liquid for food can made of aluminum |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6021443A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002010480A3 (en) * | 2000-07-28 | 2002-10-31 | Infineon Technologies Corp | Etching composition and use thereof with feedback control of hf in beol clean |
JP2021051030A (en) * | 2019-09-26 | 2021-04-01 | 三菱重工業株式会社 | Concentration monitoring system, concentration control system and concentration monitoring method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5112188A (en) * | 1974-07-19 | 1976-01-30 | Matsushita Electric Ind Co Ltd | |
JPS5459199A (en) * | 1977-10-20 | 1979-05-12 | Olympus Optical Co Ltd | Ion concentration measuring apparatus |
JPS55112560A (en) * | 1979-02-22 | 1980-08-30 | Yoshikazu Kobayashi | Ion concentration automatic measuring unit |
-
1983
- 1983-07-15 JP JP58129939A patent/JPS6021443A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5112188A (en) * | 1974-07-19 | 1976-01-30 | Matsushita Electric Ind Co Ltd | |
JPS5459199A (en) * | 1977-10-20 | 1979-05-12 | Olympus Optical Co Ltd | Ion concentration measuring apparatus |
JPS55112560A (en) * | 1979-02-22 | 1980-08-30 | Yoshikazu Kobayashi | Ion concentration automatic measuring unit |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002010480A3 (en) * | 2000-07-28 | 2002-10-31 | Infineon Technologies Corp | Etching composition and use thereof with feedback control of hf in beol clean |
JP2021051030A (en) * | 2019-09-26 | 2021-04-01 | 三菱重工業株式会社 | Concentration monitoring system, concentration control system and concentration monitoring method |
WO2021059754A1 (en) * | 2019-09-26 | 2021-04-01 | 三菱重工業株式会社 | Concentration monitoring system, concentration management system, and concentration monitoring method |
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