CN2084476U - Measuring instrument for electroplating additive - Google Patents
Measuring instrument for electroplating additive Download PDFInfo
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- CN2084476U CN2084476U CN 90222204 CN90222204U CN2084476U CN 2084476 U CN2084476 U CN 2084476U CN 90222204 CN90222204 CN 90222204 CN 90222204 U CN90222204 U CN 90222204U CN 2084476 U CN2084476 U CN 2084476U
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Abstract
The utility model relates to an electroplating solution performance detection instrument by an electrochemical method. The electrochemical method for detecting the concentration of electroplating additive is established according to the resistance and flattening effect of the additive for metal electrodeposition and the activating influence for a sedimentary layer, and an electroplating additive detection instrument is provided. The utility model is composed of a constant potential and constant current circuit, a linear sweep circuit, a press control oscillating circuit, a counting timing circuit, a second signal generator, etc. The electroplating solution performance detection instrument by an electrochemical method can quickly detect the concentration of general additive; a recorder and a microcomputer interface circuit are stocked, so the electroplating solution performance detection instrument by an electrochemical method can also detect a series of compounds with electrochemical oxidizability and reducibility. The utility model is suitable for monitoring electroplating production.
Description
The utility model relates to a kind of electroplate liquid Performance Detection instrument that adopts electrochemical method.
Electroplating additive is various in style, and with regard to bright nickel plating, the additive of having developed is above tens of kinds.The additive overwhelming majority is organic bunching thing, and the composition complexity is difficult to quantitative analysis, and plating production process replenishes by experience or with the ampere-hour consumption.As everyone knows, in the plating bath additive concentration be determined in the Electroplating Production most important.
Existing electroplating additive concentration determination is only carried out the minority additive, for example asccharin, butynediol, formaldehyde, but be limited to chemical analysis.
Cai Jiale etc. (" electroplate and environmental protection ", 1(1986) 27) and Ao Zhonghua (" plating and environmental protection " 1(1986) 29) reported also that employing spectrophotometer or mercury electrode differential capacity method measured the minority additive.
The prosperous grade of P.W.Wild(poplar man is translated " modern analysis of electroplating solution ", light industry press, 1980 the 1st edition, the 78th, 189,242 page) reported also that the employing chemical analysis measured tonka bean camphor, smart isoconcentration, use the polarography determination concentration of formaldehyde.
G.L.Fisher(Plating and Surface Finishing75 6(1988) 88) etc. also reported the concentration of measuring additive in the acid bright copper liquid with cyclic voltammetric or pulse volt-ampere method of stripping.But in the mensuration process, be subjected to the interference of plating bath composition (for example concentration of copper sulfate) bigger.
So far, most synthetic electroplating additives still can not quantitative analysis.
The purpose of this utility model is according to resistanceization and the leveling effect of additive to metal electrodeposition, and the activation of settled layer is influenced, and sets up a kind of electrochemical method of measuring additive concentration, proposes a kind of electroplating additive determinator.The concentration of the general electroplating additive of this determinator energy rapid determination also can be used to measure a series of compounds with electrochemical redox, such as the formaldehyde in the chemical bronze plating liquid, and the Fe in the plating bath
2+And Fe
3+Deng concentration.Simultaneously, be applicable to the monitoring of Electroplating Production.
This determinator comprises constant potential-constant current circuit, linear time base sweep circuit, Voltage-Controlled oscillation circuit, second signal circuit, counting and timing circuit and voltage stabilized source etc.
Constant potential-constant current circuit is the core circuit of this determinator, mainly comprises summation amplifying circuit, current-voltage conversion circuit, pilot circuit and digital voltmeter (DVM).The output of linear time base sweep circuit is connected with constant potential-constant current circuit, the current-voltage conversion circuit output of constant potential-constant current circuit connects Voltage-Controlled oscillation circuit, Voltage-Controlled oscillation circuit output is connected with the counting and timing circuit through constant potential-constant current circuit pilot circuit, and second signal circuit output is connected with the counting and timing circuit by constant potential-constant current circuit pilot circuit.
But constant potential-constant current circuit handicapping resistance parallel operation and phase inverter, constant potential exports digital voltmeter (DVM) to through impedance transformer, and continuous current exports digital voltmeter (DVM) to through phase inverter.
The counting and timing circuit is established direct display circuit and I/O interface.
Voltage-Controlled oscillation circuit is a charge balance voltage-frequency translation circuit, is made up of integrator and feedback loop.Feedback loop is made up of the fundamental mode hysteresis comparator with directivity and the analog switch that resets, and the threshold switch current potential of comparer is connected with CONTROLLED POTENTIAL.
Second signal circuit adopts crystal clock unicircuit LH5544.
The counting and timing circuit mainly is made up of up-down counter and binary-coded decimal dial switch etc.
The effect of constant potential-constant current circuit is the current potential of reference electrode when being equipped with the voltage that presets or electric current (other signals simultaneously also can superpose) with the Control Study electrode or the electric current that controlling flow is crossed electrolyzer, when measuring additive concentration, deposition on the electrode and process in leaching are all finished by this circuit.This circuit also can be used as the measurement of cathode and anode polarization curve.
Potentiostatic circuit comes down to a voltage negative feedback circuit completely.Add the linear time base sweep signal at the input terminus of operational amplifier, the signal that is recorded by reference electrode is with this signal compares and its error signal is amplified to keep reference electrode constant to the current potential of studying electrode.The precision of CONTROLLED POTENTIAL can reach 1 millivolt.Reference electrode is a kind of high impedance signal source, and not polarized in order to make reference electrode, the electric current that flows through reference electrode should be as far as possible little.This just need connect an impedance transformer on reference electrode, be connected into the voltage follower form, and output voltage is identical with the voltage that reference electrode records, and high impedance signal has been become the low resistance signal.Impedance transformer adopts high input resistance, the operational amplifier of low bias current.
Since current-to-voltage converter adopt high open-loop gain (seeing greater than 100 minutes) is arranged and than high input impedance (greater than 10
12Ohm) operational amplifier, its inverting input can be counted as ground potential (virtual earth), and the research electrode just is connected on this virtual earth, and the electric current that flows through electrolyzer so also flows through feedback resistance simultaneously, and output voltage is proportional to the electric current that flows through electrolyzer.
When constant potential-constant current circuit was worked as continuous current, sampled signal was no longer provided by the signal of reference electrode, but is provided by phase inverter, and the output voltage of phase inverter derives from the voltage of current sample.Flow through the adjusting of cell current and keep constant pilot circuit to regulate by constant potential-constant current circuit.
The linear time base sweep circuit is made up of the operational amplifier that is connected into the integration circuit form, phase inverter and comparer.Operational amplifier output is linear rises or the linear voltage that descends, by changing the speed that the RC time constant can change scanning.Stop scanning when utilizing comparer control voltage linear to scan designated value, determine stripping terminal point current potential with this.
For the electric current of the electrolyzer of will flowing through carries out numerical integration (promptly obtaining electric weight), at first current value should be become pulse number, by counter pulse number is added up then, this process is finished by voltage-controlled oscillator.The output frequency and the input voltage of voltage-controlled oscillator are linear.
The utility model to the resistanceization of metal electrodeposition and leveling effect, and to the activation influence of settled layer, has been set up the electrochemistry novel method of measuring additive concentration according to electroplating additive, replaces material in some plating bath of chemical determination with electrochemical method.This instrument can be measured the concentration of general electroplating additive, possesses manually and the function of operating automatically, and can insert the registering instrument generating writing pattern, has microcomputer interface circuit, can control automatically the electroplating process solution additive.Also can measure the leveling ability of plating bath and the leveling performance of additive, measure Fe in some plating bath
2+And Fe
3+Ionic concentration, the spending rate of additive when measure electroplating also can be used for the rapid determination of polarization curve and current efficiency.Instrument measuring speed is fast, and is easy and simple to handle.
The key technical indexes of instrument reaches: groove is pressed and is no less than ± 10V, maximum output current ± 10mA, and CONTROLLED POTENTIAL ± 2V, control current ± 10mA, reference electrode input resistance is not less than 10
12Ω, constant potential stability 1mV, continuous current stability 10 μ A, sweep velocity ± 10mV/S, electrical measurement scope 0-1C, resolving power 10
-15C, electrical measurement linearity 5 ‰, interface is measured the mode binary-coded decimal.
Fig. 1 is the circuit block diagram of this determinator.
Fig. 2 is constant potential-constant current circuit schematic diagram.
Fig. 3, for the linear time base sweep schematic circuit diagram.
Fig. 4 is the Voltage-Controlled oscillation circuit schematic diagram.
Fig. 5 is the counting and timing schematic circuit diagram.
Fig. 6 is the second signal circuit schematic diagram.
Fig. 7 is the leveling ability of nickel plating bath and the relation of additive concentration.
Fig. 8 is a leveling agent concentration C in metal deposition electric weight Qr and the plating bath
BERelation.
Fig. 9 be in the acid copper plating bath on the platinum disk electrode additive to the resistanceization of copper electrodeposition.
Figure 10 is the anodic oxidation of formaldehyde on platinum disk electrode in the chemical bronze plating liquid.
Figure 11 is the relation (max of 1gc～1g(Ia) of concentration of formaldehyde C and oxidation current maximum value (Ia) max in the chemical bronze plating liquid.
Figure 12 is the Ia～φ curve of platinum disk electrode iron ion in the iron plating bath.
Below in conjunction with embodiment and applicating example this determinator is further described.
As shown in Figure 1, this determinator comprises constant potential-constant current circuit (1-6), linear time base sweep circuit (7), Voltage-Controlled oscillation circuit (8), counting and timing circuit (9) and second signal circuit parts such as (10).
Constant potential-constant current circuit comprises summation amplifying circuit (1,2), current-voltage conversion circuit (4), impedance inverter circuit (3), voltage or current control circuit (6) and electrolyzer (5).As shown in Figure 2, during constant potential, summing amplifier A201 imports the electric potential signal that linear sweep signal and reference telegram record, reference electrode behind impedance transformer A202 feedback signal and the given signal of potentiometer P201 at operational amplifier A 201(error amplifier) compare, make the current potential of reference electrode be stabilized in set-point (the signal sum of input).IC310-313 is adapted to deposition or stripping state as constant potential continuous current change-over switch.During constant potential work, IC311,313 opens, and IC310,312 closes.When being in continuous current work, IC310,312 opens, and IC311,313 closes.Make the given current value of the electric current that flows through electrolyzer and P202 identical by IC310 regulator potentiometer P202.A202 is connected into the voltage follower form.Operational amplifier A 203 is formed current-to-voltage converter, and the electric current that flows through electrolyzer flows through feedback resistance R212 simultaneously, the output voltage U of A203
0=-iR
212So, U
0Be proportional to the electric current that flows through electrolyzer.When working as continuous current, sampled signal is no longer provided by the signal of reference electrode, but is provided by phase inverter A204.Regulate P202 and can regulate the electric current that flows through electrolyzer.
Constant potential is from the X end output of A202, and continuous current is delivered to digital voltmeter IC205 and measured from the y end output of A204.But constant potential and continuous current value independent regulation can be changed mutually in the working process automatically.
The voltage of constant potential-constant current circuit or current controller are made up of IC301-309 and dry reed relay J301, and it had both controlled constant potential-constant current circuit, also control timing and survey the electric weight circuit.K switch 201d places when presetting SET, and IC502 is in the timing number of words, puts manual I position by K switch 301a, can preset constant potential/continuous current value or stripping current potential/deposition current; When placing START, IC502 is in and countdowns, signal input second, put automatic II position by K switch 301a, switch to sedimentation state, when counting finishes (to 0), circuit automatically switches to the stripping state, when K switch 301b beat in automatic II, working order changed stripping over to by deposition, and the IC307 relay makes sweep circuit A102 from stopping to change over to scanning.
As shown in Figure 3, the linear time base sweep circuit comprises operational amplifier A 101, phase inverter A102 and comparer A103.A101 is connected into an integration circuit form, imports an electric current at inverting input, obtains linear the rising or the linear voltage that descends at output terminal, and scanning speed is regulated by the RC time constant, and (5mV/S 10mV/S), obtains by switching qli to divide second gear.When voltage linear scanned designated value, A103 turn-offed electric capacity charging input circuit (T101), thereby scanning is stopped.Regulator potentiometer P101 can regulate scanning and close power down bit, the amplitude of gated sweep, and its cycle is controlled by K101.The T102A point provides stopping of inhibit signal control counting and timing circuit count.
As shown in Figure 4, Voltage-Controlled oscillation circuit is made up of integrator A401, feedback network and 10 frequency dividing circuit IC401.Feedback network is made up of the fundamental mode hysteresis comparator A402 with directivity and the analog switch D403-406 that resets.The threshold switch current potential of comparer is not independently, eliminates the non-linear of reset circuit but be connected together with CONTROLLED POTENTIAL with the electric charge null readings.The pass of its output frequency and input voltage is f
0=KU203, wherein K=Rf/(RtRfCfEW).The conversion precision is about 0.1%.When being in the stripping working order, voltage-controlled oscillator begin output signal through the IC40110 frequency division to trip switch IC303, and deliver to digital integrator IC502, and integral result is the stripping electric weight, this electric weight can directly show or export binary-coded decimal to microcomputer by the I/O interface.
As shown in Figure 5, the main body of counting and timing circuit is up-down counter IC502, display circuit and binary-coded decimal dial switch.When up-down counter can make to subtract 1 counting reciprocal as the second timing time, as numerical integration the time, make to add 1 counting.The counting region of IC502 is 0000～9999, can directly drive common cloudy seven sections photodiodes of 0.5 English inch.When doing to subtract 1 counting, depositing time can be preset with dial switch, IC502 sends a signal during to preset time and removes to control relevant circuit.When making digital integration, count till stripping is finished one by one by the pulse signal that voltage-controlled oscillator comes.Integration finishes the back and directly reads charge value by luminotron.
IC502 has binary-coded decimal and signal output is selected in the position, can be read in by computer, gives counter end mark signal simultaneously for COMPUTER DETECTION, and the last output data of counter is latched, and is convenient to the computer reading of data like this.
As shown in Figure 6, second signal circuit adopts a crystal clock ic chip 402, and a second time reference is provided during for constant potential or continuous current electrodeposit metals.This circuit is by obtaining the square-wave signal of two group of 0.5 He Zhi to 17 frequency divisions of 32768 He Zhi, this two prescriptions ripple signal is obtained 1 second the square wave in an interval after by transistor T 401,402 combinations.Its stability is very high.
Range of application:
1, measure the leveling ability of plating bath and the leveling performance of additive, the leveling performance that is used for testing nickel, Ni-Fe, copper electrolyte additive, the best leveling concentration that records additive is consistent with the electroplating technology consumption.
2, measured the concentration and the spending rate thereof of following additive.
Acidic copper-plating of bright: Cl, Sc-1, sc-II, MN type.
Nickel plating: bright nickel, 1, the 4-butynediol, BE, 791,912, H-2, PK, asccharin.
Half bright nickel, tonka bean camphor.
High-sulfur nickel, TN-2, NS-32.
Nickel plating-iron: 791-A, XNF, asccharin.
Bright galvanization: potassium chloride type, BZ-11, ZB-85,
The zincate type, 505, ZB-80.
3, measure Fe in iron, the nickel plating bath
2+And Fe
3+Fe in ionic concentration and ferrous alloy (Ni-Fe, the zinc-iron) plating bath
2+Ionic concentration also is applicable to the iron level of measuring in Ni-Fe, the zinc-iron plating.
4, can be used for the quick measurement of determination of polarization curve and current efficiency.
Be exemplified below:
1, leveling and leveling agent concentration determination: according to leveling diffusion control theory, adopt rotating disk electrode anodic stripping method to measure the leveling ability of nickel plating bath and the relation (Fig. 7) of additive (1.4-butynediol, H-2) concentration, to be worth corresponding additive concentration scope consistent with the technology consumption in bigger leveling on the curve.Spending rate according to leveling agent in the metal electrodeposition process is proportional to its diffusion flow C
*W
1/2(C
*Be the bulk concentration of leveling agent, W is the electrode rotating speed).When the electrode invariablenes turning speed, measure leveling agent concentration C BE, linear (Fig. 8) in metal deposition electric weight Qr and the plating bath, can be used as the working curve of measuring leveling agent (or brightening agent) concentration in the plating bath.
2, the concentration determination of additive: electroplating additive often has the resistanceization effect to metal electrodeposition process, for example acid bright copper plating use, SC or additive such as MN the galvanic deposit of copper is just had resistanceization effect (Fig. 9).Curve 1 is 160g/1CuSO among the figure
45H
2O, 60g/1H
2SO
4In the plating bath of 70mg/1NaCl, platinum disk electrode (1000r/min) is gone up the I～φ curve of copper electrodeposition process, when adding mixed additive SC-I, the copper electrodeposition process is subjected to resistance (curve 2) consumingly, current potential to-0.2V deposited copper electric current reaches ultimate value, this value increases with SC-I concentration in the plating bath and reduces, experiment shows, the controlling board electrode (0.2V) is located the cathodic deposition regular hour at the current potential in limiting current district, the anodic stripping electric weight Qa of deposited copper thin layer is relevant with additive SC-I concentration in the plating bath, and SC-I concentration can get Qa and 1/C within the specific limits
SC-ILinear relationship, it can be used to measure the concentration of SC-I in the plating bath.
At nickel and Ni-Fe electrodeposition process, some sulfur-containing additive (as asccharin, benzene sulfinic acid etc.) contains in metal plating with its absorption, electrochemical reaction and changes the electrochemical therapeutic of coating, according to the influence of additive level, can be used as the concentration of measuring some sulfur-containing additive in nickel plating bath and the ferronickel plating bath to the anodic stripping voltammetry curve of settled layer.
3, chemical bronze plating liquid concentration of formaldehyde mensuration electroless copper often uses formaldehyde to make reductive agent, and the concentration of formaldehyde is generally measured with chemical analysis in the plating bath.According to formaldehyde anodised holding property on platinum electrode, can be used to measure the concentration of formaldehyde in the chemical bronze plating liquid.Figure 10 is the volt-ampere curve of formaldehyde on platinum disk electrode (500r/min) in the chemical bronze plating liquid.By curve among the figure as can be known, basal liquid (copper sulfate 10g/l+ Seignette salt 40g/l, sodium hydroxide 10g/l, PH is 12.5) in add 36% formalin, present the oxidation current of formaldehyde at the 0-+0.4V voltage belt, improve with concentration of formaldehyde, oxidation current maximum value increases, concentration of formaldehyde is the 1.5-12ml/l scope in plating bath, lgc
First-lg(Ia) max linear (Figure 11) can be used as the working curve of measuring concentration of formaldehyde in the chemical bronze plating liquid.Experiment shows, the oxidation current value of formaldehyde improves with the pH value of plating bath and increases, and therefore, the pH value of the PH that need regulate liquid to be measured during mensuration in advance during with the making working curve is identical.
4, mineral ion concentration determination Figure 12 is the I～φ curve of platinum disk electrode (1000r/min) in iron plating liquid, records Fe
2+Anodic oxidation limiting current and Fe
3+The cathodic reduction limiting current and plating bath in iron concentration linear, it can be used as measures Fe in the plating bath
2+And Fe
3+The working curve of ionic concn.Experiment shows that this method also is applicable to the mensuration of iron concentration in nickel plating bath and the ferrous alloy plating bath.In addition, oxidation current value and the chlorine ion concentration of test platinum dish (2000r/min) electrode in acid copper plating bath is linear, can be used as the working curve of measuring chlorine ion concentration in the plating bath.
Claims (6)
1, a kind of electroplating additive determinator, it is characterized in that comprising constant potential-constant current circuit, the linear time base sweep circuit, Voltage-Controlled oscillation circuit, second signal circuit, counting and timing circuit and voltage stabilized source etc., said constant potential-constant current circuit comprises summing amplifier, current-voltage conversion circuit, pilot circuit, digital voltmeter (DVM) and electrolyzer, the output of linear time base sweep circuit is connected with the input terminus of summing amplifier, the current-voltage conversion circuit output of constant potential one constant current circuit connects Voltage-Controlled oscillation circuit, and the output of Voltage-Controlled oscillation circuit is connected with the counting and timing circuit with the pilot circuit of the output of second signal circuit through constant potential-constant current circuit.
2, determinator as claimed in claim 1, but it is characterized in that constant potential one constant current circuit handicapping resistance parallel operation and phase inverter, constant potential is exported through impedance transformer, and continuous current exports digital voltmeter (DVM) to through phase inverter and measures.
3, determinator as claimed in claim 1 is characterized in that the linear time base sweep circuit is made up of the operational amplifier that is connected into the integration circuit form, phase inverter and comparer.
4, determinator as claimed in claim 1 is characterized in that Voltage-Controlled oscillation circuit is made up of integrator, fundamental mode hysteresis comparator and the feedback loop and 10 frequency dividing circuits of the analog switch that resets with directivity.
5, determinator as claimed in claim 1 is characterized in that the counting and timing circuit is made up of up-down counter, binary-coded decimal dial switch and display circuit.
6, determinator as claimed in claim 5 is characterized in that the counting and timing circuit is provided with the I/O interface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90222204 CN2084476U (en) | 1990-10-09 | 1990-10-09 | Measuring instrument for electroplating additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90222204 CN2084476U (en) | 1990-10-09 | 1990-10-09 | Measuring instrument for electroplating additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2084476U true CN2084476U (en) | 1991-09-11 |
Family
ID=4900189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90222204 Withdrawn CN2084476U (en) | 1990-10-09 | 1990-10-09 | Measuring instrument for electroplating additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN2084476U (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337111C (en) * | 2001-10-01 | 2007-09-12 | G·恰雷特 | Improved method for analysis of three organic additives in an acid copper plating bath |
| CN110455904A (en) * | 2019-07-05 | 2019-11-15 | 九江德福科技股份有限公司 | The quantitative analysis method of brightener in a kind of electrolyte of copper foil |
| CN112630268A (en) * | 2020-11-26 | 2021-04-09 | 燕山大学 | Bipolar miniature ion concentration sensor and measurement system thereof |
-
1990
- 1990-10-09 CN CN 90222204 patent/CN2084476U/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337111C (en) * | 2001-10-01 | 2007-09-12 | G·恰雷特 | Improved method for analysis of three organic additives in an acid copper plating bath |
| CN110455904A (en) * | 2019-07-05 | 2019-11-15 | 九江德福科技股份有限公司 | The quantitative analysis method of brightener in a kind of electrolyte of copper foil |
| CN110455904B (en) * | 2019-07-05 | 2022-08-23 | 九江德福科技股份有限公司 | Quantitative analysis method for brightener in copper foil electrolyte |
| CN112630268A (en) * | 2020-11-26 | 2021-04-09 | 燕山大学 | Bipolar miniature ion concentration sensor and measurement system thereof |
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