CN1048452A - Laser microanalysis instrument - Google Patents
Laser microanalysis instrument Download PDFInfo
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- CN1048452A CN1048452A CN 89104227 CN89104227A CN1048452A CN 1048452 A CN1048452 A CN 1048452A CN 89104227 CN89104227 CN 89104227 CN 89104227 A CN89104227 A CN 89104227A CN 1048452 A CN1048452 A CN 1048452A
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Abstract
The invention discloses a kind of laser microanalysis instrument, mainly form by small enclosed ultraviolet pulse laser and metering circuit system, this metering circuit system not only can carry out time resolution, and do the A/D conversion after can repeatedly adding up signal, can also be by changing optical filter to adapt to the needs of different emission wavelengths, measuring system is synchronous with laser instrument, can direct-reading go out data and the laser intensity data that are directly proportional with measured matter content, also can be connected with micro computer and carry out data processing by the counting machine interface of standard.Can be widely used in geological prospecting, chemical prospecting, environmental protection, departments such as medical treatment, biomedicine or Food Inspection.
Description
The present invention relates to a kind of instrument that utilizes the LASER-TIME RESOLVED fluorometry to measure trace materials content in the solution example, is a kind of laser microanalysis instrument specifically.
The LASER-TIME RESOLVED fluorometry is a kind of brand-new analytical technology that grows up the nearly more than ten years, is just studied widely and uses.Canada first Dary company produced a kind of UA-3 uranium analyser (seeing UA-3 Uranium Analyser) in 1978, and it is to utilize the laser excitation uranium sample, produces fluorescence, measures the content that the uranium fluorescence intensity is measured uranium in the solution example.But, this analyser is in its major part, be not have time delay, Measuring Time and the variable control circuit of measurement cumulative number in the metering circuit system, do not adapt to the optical system of surveying different emission wavelengths, promptly can not measure the content of other micro substances in the solution according to different material luminescent lifetime and difference of wavelength, can only under the condition of fixing time delay and Measuring Time and fixing uranium wavelength of fluorescence, measure the content of uranium, so limited the usable range of this analyser.
The objective of the invention is to design a kind of can be according to different material luminescent lifetime and wavelength different, the measured matter emission wavelength is being selected again it is carried out the LASER-TIME RESOLVED fluorescence measurement on the basis, had that selectivity is good, highly sensitive, precision is high, an applied range, reliable and stable laser microanalysis instrument.
The present invention is achieved in that laser microanalysis instrument is made up of sample measuring device, laser component, laser circuit system, photoelectrical coupler and metering circuit system.Said laser component adopts a small enclosed ultraviolet pulse laser, said metering circuit system comprises the fluorescence signal acquisition cuicuit, the fluorescence linear gate that links to each other with this circuit output end, the A/D converter that links to each other with the linear gate output terminal of fluorescence, this A/D converter is provided with the fluorescence intensity display, the laser signal acquisition cuicuit, the laser linear gate that links to each other with this circuit output end, the A/D converter that is connected with the laser linear gate, this A/D converter also is provided with the laser intensity display, and the fluorescence sampling control signal produces circuit, the laser sampling control signal produces circuit, time delay and Measuring Time produce circuit and governor circuit.Wherein, link to each other with input end that fluorescence sampling control signal produce circuit with the output terminal that Measuring Time produces circuit time delay, the fluorescence sampling control signal produces another input end of the output termination photoluminescence line door of circuit, the laser sampling control signal produces another input end of the output termination laser rays door of circuit, the output terminal of the input termination photoelectrical coupler of governor circuit, an output terminal of governor circuit produces circuit with the fluorescence sampling control signal respectively and is connected with the input end that the laser sampling control signal produces circuit, and its another output terminal connects the input end of fluorescence A/D converter and laser A/D converter respectively.Said sample measuring device is provided with optical filter and changes parts.
Selected time delay and Measuring Time are inserted time delay and Measuring Time generation circuit, in this circuit, demonstrate this and insert data, press starting switch, signal from laser component produces main signal through photoelectric coupler output end by governor circuit, this signal makes the fluorescence sampling control signal produce circuit on the one hand and the laser sampling control signal produces circuit generation fluorescence and laser sampled signal, when the number of the main signal that produces when governor circuit equals predefined measurement cumulative number on the other hand, governor circuit is also exported an A/D changeover control signal, control two A/D converters fluorescence that has added up and laser intensity are converted to digital quantity, and on display separately, show.
This shows that metering circuit of the present invention system not only can carry out time resolution, but also do the A/D conversion after can repeatedly adding up signal, read the fluorescence intensity that is directly proportional with measured matter content synchronously and be used for the laser intensity data of excited sample; Adopt and change the optical filter way, can measure different emission wavelengths; Can also be connected with micro computer by the interface of standard computer simultaneously, carry out data processing.
Now in conjunction with the accompanying drawings and embodiments the present invention is done and is described in further detail:
Fig. 1 is the block diagram of laser microanalysis instrument;
Fig. 2 is laser component and laser circuit system chart;
Fig. 3 is the metering circuit system chart;
Fig. 4 is that time delay and Measuring Time produce circuit diagram;
Fig. 5 is the governor circuit synoptic diagram;
Fig. 6 is that the fluorescence sampling control signal produces circuit diagram;
Fig. 7 is that the laser sampling control signal produces circuit diagram;
Fig. 8 is the A/D converter synoptic diagram.
As shown in Figure 1, laser microanalysis instrument is made up of sample measuring device 1, laser component 2, laser circuit system 3, photoelectrical coupler 4 and metering circuit system 5.
The structure of sample measuring device 1 is known, it comprises laser focusing mirror and catoptron, saturating ultraviolet filter, measure darkroom and the planchet that places in the darkroom, because different material excites the wavelength of fluorescence difference of generation, so become 90 ° position to be provided with the window of replaceable fluorescent optical filter in the planchet outside with the laser emitting direction,, change different optical filters according to emission wavelength, select useful signal, improve the selectivity of instrument.
Fig. 2 shows laser component and laser circuit system, and laser component 2 is by laser tube 2-1, thyratron 2-2, resistance R
1And R
2, capacitor C
1And C
2Be formed by connecting by known circuit, and C1 and C2 all are formed in parallel by the noninductive electric capacity of a plurality of high pressure, and laser instrument is the small enclosed ultraviolet pulse laser, and light impulse length is about 5 nanoseconds, instantaneous power is 15～20 kilowatts, and the output optical pulse wavelength mainly is 3371
, still have 3577 in addition
With 3805
Deng, glow frequency is 12～15Hz.Because the instantaneous power height, and can focus on light pulse on the luminous point, so the material low to those luminescence efficiencys still has the quite high sensitivity that excites.
The closed ultraviolet pulse laser of this instrument could be worked after four minutes so give heat owing to adopted thyratron ZQM-50/5 to do pulse forming switch.After the preheating, send a timing controlled level here by timing circuit, this level is added to the control circuit 6-1 that is made up of 1/4CO36, and the clock signal of having only the clock circuit 7 at this moment be made up of 3/4CO36 to send here just can be delivered to the control circuit 6-2 that is made up of 1/2CO43.The control level of control circuit 6-2 output is delivered to the high-voltage oscillation device of being made up of CO36 8 again, and makes it work.If laser switch K connects, then will make circuit for producing high voltage 9 work of forming by 3DG27 * 2, DF104 * 2, interstage transformer, high-tension transformer, capacitance resistance ware and some diodes, two voltage-multiplying circuits, 10 multiplication of voltages of being made up of 2CLG * 2 and electric capacity are delivered in its output again, form the laser high pressure, deliver to laser component 2.In addition, along with the formation of laser high pressure, the sample circuit 11 that is formed by electric resistance partial pressure feeds back to sampled signal the comparator circuit of being made up of CH3130 12.When sampling voltage was higher than the normal voltage of normal voltage generation circuit 16 generations, comparator circuit 12 states were changed, and control circuit 6-2 is delivered in its output, caused the output state of control circuit 6-2 to change, so high-voltage oscillation device 8 failure of oscillations.The laser high pressure is held on the capacitor C 1 and C2 of laser component 2.The monostable circuit 13 that the clock signal that clock circuit 7 is sent is also formed via 1/2J210 is done the delay of 20～40 microseconds, to be shaped to width be that the square wave of 40 microseconds is delivered to photoelectrical coupler 4 to the monostable circuit of forming via other 1/2J210 on the one hand 14 afterwards, also delivers to lock grid trigger pip on the other hand and form circuit 15 and form thyratron grid trigger pips and deliver to the thyratron grid.It is by the 2/4CO33 parallel connection that this lock grid trigger pip forms circuit 15, and 3DA87T, 2CLG and some resistance, electric capacity and a high Q value inductance are formed.The arrival of lock gate signal makes the thyratron conducting, so Laser Devices form laser.Laser tube glow discharge simultaneously, loss of voltage on Laser Devices capacitor C 1 and the C2, sample circuit 11 sampling voltages return to zero, cause comparator circuit 12 to return to original state again, the output control voltage of control circuit 6-2 makes 8 work of laser high-voltage oscillation circuit again, forms the laser high pressure again.So constantly circulation forms a succession of laser pulse output.
As shown in Figure 3, the metering circuit system is by fluorescence signal acquisition cuicuit 17, the fluorescence linear gate 18 that links to each other with this circuit output end, the A/D converter 19 that links to each other with fluorescence linear gate 18 output terminals, this A/D converter is provided with fluorescence intensity display 20, laser signal acquisition cuicuit 21, the laser linear gate 22 that links to each other with this circuit output end, the A/D converter 23 that is connected with laser linear gate 22, this A/D converter also is provided with laser intensity display 24, the fluorescence sampling control signal produces circuit 25, the laser sampling control signal produces circuit 26, time delay and Measuring Time produce circuit 27 and governor circuit 28 is formed.Link to each other with input end that fluorescence sampling control signal produce circuit 25 with the output terminal that Measuring Time produces circuit 27 time delay, the fluorescence sampling control signal produces another input end of the output termination photoluminescence line door 18 of circuit 25, the laser sampling control signal produces another input end of the output termination laser rays door 22 of circuit 26, the output terminal of the input termination photoelectrical coupler 4 of governor circuit 28, an output terminal of governor circuit 28 produces circuit 25 with the fluorescence sampling control signal respectively and is connected with the input end that the laser sampling control signal produces circuit 26, and its another output terminal connects the input end of fluorescence A/D converter 19 and laser A/D converter 23 respectively.
In the present embodiment, fluorescence signal acquisition cuicuit 17 is by photomultiplier GDB-23T, and transistor and operational amplifier FCO54 form, and photomultiplier obtains fluorescence signal, output after the amplifier of transistor coupling and operational amplifier FCO54 composition amplifies; Laser signal acquisition cuicuit 21 is made up of silicon photocell and operational amplifier CH3130, and silicon photocell converts laser signal to electric signal, output after the amplifier that operational amplifier CH3130 forms amplifies.Deliver to the known sample circuit of being made up of two linear gates after the amplifier output of two amplifier FCO54, CH3130 compositions and take a sample, sampled signal is sent into two identical A/D converters 19 and 23 respectively and is carried out the A/D conversion.
As shown in Figure 4, time delay and Measuring Time generation circuit comprises by a 10/BCD code coder C304 and ten key-to-disk 27-1 that button is formed.By CH283 * 8(is SCR301 * 8) and CH4081 be composed in series deposit display 27-2, by C187, CO32, J210, CO39, and the sequential square wave generation circuit 27-3 that forms of CD4071 and the 1KHz driven sweep device 27-4 that forms by CO36 and CO43.Button is connected according to a conventional method with scrambler C304, and the output terminal of scrambler C304 is connected with an input end depositing display 27-2, and the output terminal of key-to-disk 27-1 also links to each other with the input end of sequential square wave generation circuit 27-3 simultaneously simultaneously.The output termination of sequential square wave generation circuit 27-3 and driven sweep device 27-4 is deposited the input end of display 27-2.
Key-to-disk 27-1 output binary-coded decimal is delivered to and is deposited among the display 27-2, decimal system number of every key input, while key-to-disk 27-1 also produces one and send the pulse of numerical control system to make sequential square wave generation circuit 27-3 produce a corresponding received signal, by its corresponding output line 0.1.2. ... 8 binary-coded decimals receive to be deposited display 27-2 and goes up corresponding positions and deposit and show, show totally eight, wherein four display delay times, four show Measuring Time in addition.The keyboard input is to carry out by turn, in order to reduce power consumption, adopts 1KHz driven sweep device 27-4 to drive and shows.Deposit that CH283 can also do the nonsignificant zero blanking among the display 27-2.
The major function of governor circuit 28 is to produce main signal to make the fluorescence sampling control signal produce circuit 25 and 26 work of laser sampling control signal generation circuit, produces an A/D changeover control signal according to predetermined accumulative total measurement number of times when accumulative total finishes simultaneously.As shown in Figure 5, governor circuit 28 comprises the R-S trigger 28-1 that is made up of 1/2CO43, the binary counter 28-2 that forms by 1/2CO43, form by 1/4CH4081 with door 28-3,28-4,28-5,28-6, the Sheffer stroke gate 28-7 that forms by 1/4CO36,28-8,28-9,28-10, that form by 1/4CH4071 or the door 28-11,28-12,28-13,28-14, the binary counter 28-15 that is barricaded as by 1/2CO43, that form by CH4071 or the door 28-16,28-17, the ÷ 100 circuit 28-18 that two-stage C187 forms, the monostalbe trigger 28-19 and the start key A that form by 1/2J210, stop key B, reset key C, single-repetition switch K, resistance R 1, R2, R3, R4, R5, R6, R7, R8, R9, R10, capacitor C 4, C5, C7, C8, C9 and diode D.Stop key B and resistance R 2 link to each other the back with or the input end of a 28-13 be connected, or the output terminal of door 28-13 is connected with the R input end of R-S trigger 28-1, the Q output termination of R-S trigger 28-1 and the input end of door 28-4, reset key C with after resistance R 3 links to each other respectively with the R input end of binary counter 28-2 and or door 28-14, the input end of 28-17 connects, or the output terminal of door 28-17 is connected with the Tr input end of monostalbe trigger 28-19, the 2Hz input end of the logic controller 19-11 of the Q output termination A/D converter of monostalbe trigger 28-19, output terminal with the input termination photoelectrical coupler 4 of door 28-3 and 28-5, S input end with the output termination R-S trigger 28-1 of door 28-3, the Q output termination of R-S trigger 28-1 and another input end of door 28-5, connect respectively and door 28-6 with the output terminal of door 28-5, Sheffer stroke gate 28-7, the input end of 28-8 and 28-9, two input ends of the output termination Sheffer stroke gate 28-10 of Sheffer stroke gate 28-9, the output terminal of Sheffer stroke gate 28-8 and 28-10 connects respectively behind separately R-C differentiating circuit R8-C8 and R9-C9 or two input ends of door 28-12, or the input end of the output termination of door 28-12 or door 28-11, or the EN input end of the output termination ÷ 100 circuit 28-18 of door 28-11, the CL end of the output termination binary counter 28-2 of ÷ 100 circuit 28-18, the Q output terminal of binary counter 28-2 connects another input end with door 28-6 and Sheffer stroke gate 28-7 respectively, and through a R7-C7 differentiating circuit connect or the door 28-16 an input end, its Q output terminal connects another input end of Sheffer stroke gate 28-8 and 28-9 respectively, connect through the R4-C4 differentiating circuit simultaneously or another input end of door 28-17, or the output terminal of door 28-16 connects the R input end of binary counter 28-15 and ÷ 100 circuit 28-18 respectively, the CL input end of the output termination binary counter 28-15 of Sheffer stroke gate 28-7, another input end of the output termination of binary counter 28-15 or door 28-11, connect fluorescence sampling control signal generation circuit 25 and the input end of laser sampling control signal generation circuit 26 and the R-S trigger 19-10 input end in the A/D converter 19 respectively with the output terminal of door 28-6, the Q output terminal of monostalbe trigger 28-19 connects the end of single-repetition switch K behind the R5-C5 differentiating circuit, the cutter of single-repetition switch K connects the positive pole of diode D, the negative pole of diode D respectively with or another input end of door 28-13 and 28-14 is connected, start key A connects resistance R 1 afterwards and be connected with another input end of door 28-4.
Governor circuit 28 principle of work are as follows:
Press stop key B, warp or door 28-13 open and a 28-4 Q end output high level of R-S trigger 28-1, press reset key C afterwards, then binary counter 28-15 and ÷ 100 circuit 28-18 and all zero clearings of R-S trigger 28-1, monostalbe trigger 28-19 exports a square wave simultaneously, makes A/D converter 19 and 23 carry out an A/D conversion.When pressing start key A, make Q end output the becoming high level of R-S trigger 28-1 on the one hand from the square wave of photoelectrical coupler 4, open and door 28-5, make this square wave by being added to and door 28-6 and Sheffer stroke gate 28-7 simultaneously with door 28-5, on 28-8 and the 28-9, but owing to the Q end of binary counter 28-2 when zero clearing has become high level, its Q end is low level, so have only Sheffer stroke gate 28-8 and 28-9 to open, and with door 28-6, Sheffer stroke gate 28-7 closes, cause with the door 28-5 the output square wave can only pass through Sheffer stroke gate 28-8 and 28-9, Sheffer stroke gate 28-10, or the effect of door 28-12 is respectively through separately R-C circuit R8-C8 the forward position of above-mentioned square wave and back edge, two spike pulses that form behind the R9-C9 differential be shaped to two pulses by or a door 28-11 be ÷ 100 circuit 28-18 counting, when ÷ 100 circuit 28-18 count down to predetermined value, its output makes binary counter 28-2 change state, this moment, the Q end of binary counter 28-2 became high level, the Q end is low level, so, open with door 28-6 and Sheffer stroke gate 28-7, Sheffer stroke gate 28-8 and 28-9 close, when the Q of binary counter 28-2 end becomes high level by low level, also make or the output of door 28-16 generation positive pulse by the R7-C7 differentiating circuit, thus, binary counter 28-15 and ÷ 100 circuit 28-18 are cleared again.Because with door 28-6, Sheffer stroke gate 28-7 is opened, when next square wave with door 28-5 is exported, make and producing main signal with door 28-6 output terminal, send the fluorescence sampling control signal to produce circuit 25 and laser sampling control signal generation circuit 26, and by Sheffer stroke gate 28-7 and or door 28-11 ÷ 200 rolling counters forwards of forming for binary counter 28-15 and ÷ 100 circuit 28-18, when counting down to predetermined value, the output of ÷ 100 circuit 28-18 has changed the state of binary counter 28-2 again, then cause and not gate 28-8 and 28-9 are opened, with door 28-6, Sheffer stroke gate 28-7 closes, and makes binary counter 28-15 and ÷ 100 circuit 28-18 zero clearings.In addition, the Q output terminal of binary counter 28-2 by low level become high level positive transition differential positive signal by or door 28-17 trigger monostalbe trigger 28-19, so monostalbe trigger 28-19 produces an A/D changeover control signal.Obviously, when being opened, equal the count value of being scheduled to just, so constantly move in circles with the main signal number of door 28-6 output with door 28-6 and Sheffer stroke gate 28-7.If carry out single measurement, then monostalbe trigger 28-19 Q output through the differential positive signal of differentiating circuit R5-C5 through diode D and or door 28-13 feed back to the R end of R-S trigger 28-1, make it become the Q state and just can.
As shown in Figure 6, the fluorescence sampling control signal produces circuit 25 and comprises a R-S trigger 25-1 who is made up of CO43, the 1MHz oscillator 25-2 that 2/4CO36 forms, a level Four of being made up of four C182 cascades can preset several frequency dividers/divider 25-3, two binary counter 25-4 and 25-5 that form by CO43, one that compose in parallel by four C540 with or switch 25-6, each C540 transmits a group delaing time and Measuring Time, its KA control propagation delay time, KB control transmits Measuring Time, be made up of a 1/4CH4071 or door 25-7, the phase inverter 25-8 that CO36 forms.Or the output terminal of door 25-7 connects R-S trigger 25-1 respectively, the R end of binary counter 25-4 and 25-5, the Q of binary counter 25-5 and Q output terminal connect respectively with or switch 25-6 KA at different levels and KB end, with or eight of switch 25-6 put several input ends (each puts several input ends four binary-coded decimal incoming lines) eight output terminals corresponding and be connected with depositing display 27-2, its output terminal connects several input ends of putting of frequency divider/divider 25-3 respectively, " 0 " output terminal of frequency divider/divider 25-3 connects the input end of phase inverter 25-8 and the CL input end of binary counter 25-4 respectively, the output terminal of phase inverter 25-8 connects the CL end of binary counter 25-5, the S of R-S trigger 25-1 input termination governor circuit 28 with output terminal door 28-6, the input end of its Q output termination oscillator 25-2, the input end of output termination frequency divider/divider 25-3 of oscillator 25-2, the control input end of the Q output termination photoluminescence line door 18 of binary counter 25-4, the input end of its Q output termination or door 25-7, or the zero setting output terminal of another input termination governor circuit 28 of door 25-7.
The fluorescence sampling control signal produces the circuit working principle: at first the reset signal by or door 25-7 R-S trigger 25-1 and binary counter 25-4 and 25-5 are set to the Q state, wherein, the Q of binary counter 25-5 be high level send with or the KA of switch 25-6 end, by with or switch 25-6 respectively put several input ends to what deliver to frequency divider/divider 25-3 time delay, and data are delivered in frequency divider/divider 25-3, when frequency divider/divider 25-3 receives this data, its first order " 0 " output terminal is by high level step-down level, this negative level saltus step is inoperative to binary counter 25-4, but 25-8 is inverted into positive transition by phase inverter, make binary counter 25-5 change state, be that its Q output terminal becomes high level, the Q end becomes low level, promptly with or the KB of switch 25-6 become high level, KA becomes low level.Thus by with or converter switch 25-6 the Measuring Time data are delivered to several input ends of putting of frequency divider/divider 25-3, but can not deliver to these data in frequency divider/divider 25-3 this moment, this is inserting owing to time delay, make the gating end of frequency divider/divider 25-3 become low level cause, if make the Q output terminal of R-S trigger 25-1 become high level but send a main signal here this moment, then oscillator 25-2 starting of oscillation, frequency divider/divider 25-3 just begins counting.When being kept to zero the time delay in frequency divider/divider 25-3, its first order " 0 " output terminal becomes high level again, at once Measuring Time is inserted in frequency divider/divider 25-3, make it continue to do subtraction, but when Measuring Time wherein reduces to zero, its " 0 " output terminal becomes high level by low level, causes binary counter 25-4 to change state again, and promptly its Q end becomes low level by high level.The Q output terminal of binary counter 25-4 is sent a square wave and is delivered to fluorescence linear gate 18 thus, this square wave zero-time equals time delay just apart from the main signal width, and self width equals Measuring Time just, the Q of binary counter 25-4 end output positive transition simultaneously by or door 25-7 R-S trigger 25-1, binary counter 25-4 and 25-5 are set to original state, and the primary sample control signal produces and finishes.After this main signal that has another one, above-mentioned circulation is proceeded.
As shown in Figure 7, the laser sampling control signal produces circuit 26 and adopts two monostable trigger 26-1 of J210 and 26-2 to form, laser is fixed sample time, monostalbe trigger 26-1 produces 100 microseconds to postpone, afterwards with one 100 wide laser sampling control signal of microsecond of monostalbe trigger 26-2 output.
In the present embodiment, laser A/D converter 23 adopts identical circuit with fluorescence A/D converter 19.As shown in Figure 8, fluorescence A/D converter 19 comprises 4 1/2 double integration A/D conversion logics of CH259 controller 19-11, CH3130 operational amplifier 19-1 and 19-2, C544 linear gate 19-3,19-4,19-5,19-6,19-7,19-8, the R-S trigger 19-10 that monostable circuit 19-9 that 1/2CO43 forms and 1/2CO43 form, logic controller 19-11, operational amplifier 19-1,19-2, linear gate 19-6,19-7,19-8 forms one from steady zero integral device, two input ends of linear gate 19-3 connect the Q output terminal of fluorescence signal acquisition cuicuit 17 and fluorescence sampling control signal generation circuit 25 binary counter 25-4 respectively, linear gate 19-3,19-4, after linking to each other, the 19-5 output terminal connects input end from steady zero integral device, the K2 of logic controller 19-11, K3, the K4 output terminal connects linear gate 19-4 respectively, the CL end of the input end of 19-5 and monostable circuit 19-9, the Q output terminal of monostable circuit 19-9 connects the input end of linear gate 19-8, its Q output terminal connects the S input end of R-S trigger 19-10 through a R-C differentiating circuit, the Q output terminal of R-S trigger 19-10 connects the input end of linear gate 19-6 and 19-7 respectively, the R input end of R-S trigger 19-10 is connected with the output terminal with door 28-6 of governor circuit 28 through a R-C differentiating circuit, and the 2Hz input end of logic controller 19-11 connects the Q output terminal of the monostalbe trigger 28-19 of governor circuit 28.
The A/D converter principle of work is: behind the K4 signal triggering monostable circuit 19-9 from logic controller 19-11, the positive square wave of its Q end output makes from steady zero integral device and makes zero, its Q end output signal triggers into the Q state to R-S trigger 19-10 behind differential simultaneously, the Q end output high level of R-S trigger 19-10 is opened linear gate 19-6 and 19-7, make from steady zero integral device from steady zero, the input of main signal makes R-S trigger 19-10 convert the Q state to again, its Q end becomes low level, linear gate 19-6 and 19-7 are closed, stop from steady zero, the sampling control signal of fluorescence one by one that comes after main signal is opened linear gate 19-3 one by one, just carry out successive integration from steady zero integral device, and then send the 2Hz input end that the A/D changeover control signal is added to logic controller 19-11 here, then carry out the A/D conversion, according to the polarity of input signal before this, logic controller 19-11 exports corresponding K2 or K3 controls from steady zero integral device to anti-phase integration, when treating that anti-phase integration makes zero, logic controller 19-11 output K4 signal, this moment, an A/D converted, then the LED charactron that links to each other with logic controller 19-11 demonstrates fluorescence measurements, show the driving circuit that uses 5G1413 to form in this circuit in order to promote LED charactron 19-13.
This instrument can be according to the fluorescence lifetime difference of different material 10
-6～10
-2Change time delay and Measuring Time in seconds four order magnitude range, and can system measure measured matter at this moment between fluorescence lifetime curve in the scope.Can reach requirement according to the fluorescence efficiency of measured matter, in 20,40,60,80,100,120,140,160,180 and 200 ten grades of scopes, change each cumulative number of measuring measuring accuracy.
Reached the following lower limit that detects when utilizing this instrument that some material is done trace measurement:
Uranium: 10ppt; Boron: 10ppt; Europium: 0.1ppt; Samarium: 0.3ppt; Dysprosium: 4ppt; Terbium: 6ppt.In addition, to thorium, palladium, zirconium, hafnium etc. detect lower limit all less than 1ppb, to the negative ion that generally is difficult to measure,, also obtain very desirable analytical effect as chlorate anions.Utilize this instrument can also carry out immunoassay, especially for radiommunoassay, this instrument can fundamentally be eliminated radioactive contamination, has also solved the not good problem of radioimmunology analysis stability.Therefore this instrument can be widely used in departments such as geological prospecting, chemical prospecting, environmental protection, health care, biomedicine or Food Inspection.
Claims (5)
1, a kind of laser microanalysis instrument, by sample measuring device 1, laser component 2, laser circuit system 3, photoelectrical coupler 4 and metering circuit system 5 form, it is characterized in that said laser component 2 adopts a small enclosed ultraviolet pulse laser, said metering circuit system 5 is by fluorescence signal acquisition cuicuit 17, the fluorescence linear gate 18 that links to each other with this circuit output end, the A/D converter 19 that links to each other with fluorescence linear gate 18 output terminals, this A/D converter is provided with fluorescence intensity display 20, laser signal acquisition cuicuit 21, the laser linear gate 22 that links to each other with this circuit output end, the A/D converter 23 that links to each other with laser linear gate 22, this A/D converter also is provided with laser intensity display 24, the fluorescence sampling control signal produces circuit 25, the laser sampling control signal produces circuit 26, time delay and Measuring Time produce circuit 27 and governor circuit 28 is formed, link to each other with input end that fluorescence sampling control signal produce circuit 25 with the output terminal that Measuring Time produces circuit 27 time delay, the fluorescence sampling control signal produces output terminal that circuit 25 and laser sampling control signal produce circuit 26 and is connected with another input end of 22 with linear gate 18 respectively, the output terminal of the input termination photoelectrical coupler 4 of governor circuit 28, an one output terminal produces circuit 25 with the fluorescence sampling control signal respectively and is connected with the input end that the laser sampling control signal produces circuit 26, its another output terminal connects the input end of A/D converter 19 and 23 respectively, and said sample measuring device is provided with optical filter and changes parts.
2, according to the said a kind of laser microanalysis instrument of claim 1, it is characterized in that described time delay and Measuring Time produce circuit 27 and comprise by a 10/BCD code coder C304 and ten key-to-disk 27-1 that button is formed, by CH283 * 8(is SCR301 * 8) and CH4081 be composed in series deposit display 27-2, by C187, CO32, J210, CO39, and the sequential square wave generation circuit 27-3 of CD4071 composition and the 1KHz driven sweep device 27-4 that forms by CO36 and CO43, the output terminal of the scrambler C304 of key-to-disk 27-1 is connected with an input end depositing display 27-2, the output terminal of key-to-disk 27-1 also links to each other with the input end of sequential square wave generation circuit 27-3, and the output termination of sequential square wave generation circuit 27-3 and driven sweep device 27-4 is deposited the input end of display 27-2.
3, a kind of laser microanalysis instrument according to claim 1, it is characterized in that described governor circuit 28 comprises the R-S trigger 28-1 that is made up of 1/2CO43, the binary counter 28-2 that forms by 1/2CO43, form by 1/4CH4081 with door 28-3,28-4,28-5,28-6, the Sheffer stroke gate 28-7 that forms by 1/4CO36,28-8,28-9,28-10, that form by 1/4CH4071 or the door 28-11,28-12,28-13,28-14, the binary counter 28-15 that is barricaded as by 1/2CO43, that form by CH4071 or the door 28-16,28-17, the ÷ 100 circuit 28-18 that two-stage C187 forms, the monostalbe trigger 28-19 and the start key A that form by 1/2J210, stop key B, reset key C, single-repetition switch K, resistance R 1, R2, R3, R4, R5, R6, R7, R8, R9, R10, capacitor C 4, C5, C7, C8, C9 and diode D, stop key B and resistance R 2 link to each other the back with or the input end of a 28-13 be connected, or the output terminal of door 28-13 is connected with the R input end of R-S trigger 28-1, the Q output termination of R-S trigger 28-1 and the input end of door 28-4, reset key C with after resistance R 3 links to each other respectively with the R input end of binary counter 28-2 and or door 28-14, the input end of 28-17 connects, or the output terminal of door 28-17 is connected with the Tr input end of monostalbe trigger 28-19, the 2Hz input end of the Q output termination A/D converter 19 of monostalbe trigger 28-19 and 23 logic controller 19-11, an output terminal of importing termination photoelectrical coupler 4 with door 28-3 and 28-5, S input end with the output termination R-S trigger 28-1 of door 28-3, the Q output termination of R-S trigger 28-1 and another input end of door 28-5, connect respectively and door 28-6 with the output terminal of door 28-5, Sheffer stroke gate 28-7, the input end of 28-8 and 28-9, two input ends of the output termination Sheffer stroke gate 28-10 of Sheffer stroke gate 28-9, the output terminal of Sheffer stroke gate 28-8 and 28-10 is through separately R-C differentiating circuit R8-C8, connect respectively behind the R9-C9 or the door 28-12 two input ends, or the input end of the output termination of door 28-12 or door 28-11, or the EN input end of the output termination ÷ 100 circuit 28-18 of door 28-11, the CL end of the output termination binary counter 28-2 of ÷ 100 circuit 28-18, the Q output terminal of binary counter 28-2 connects another input end with door 28-6 and Sheffer stroke gate 28-7 respectively, and through a R7-C7 differentiating circuit connect or the door 28-16 an input end, its Q output terminal connects another input end of Sheffer stroke gate 28-8 and 28-9 respectively, and process R4-C4 differentiating circuit connects or another input end of door 28-17, or the output terminal of door 28-16 connects the R input end of binary counter 28-15 and ÷ 100 circuit 28-18 respectively, the CL input end of the output termination binary counter 28-15 of Sheffer stroke gate 28-7, another input end of the output termination of binary counter 28-15 or door 28-11, meet fluorescence sampling control signal generation circuit 25 and the input end of laser sampling control signal generation circuit 26 and the R-S trigger 19-10 in the A/D converter 19 respectively with the output terminal of door 28-6, the Q output terminal of monostalbe trigger 28-19 connects the end of single-repetition switch K behind the R5-C5 differentiating circuit, the cutter of single-repetition switch K connects the positive pole of diode D, the negative pole of diode D respectively with or another input end of door 28-13 and 28-14 is connected, start key A connects resistance R 1 afterwards and be connected with another input end of door 28-4.
4, a kind of laser microanalysis instrument according to claim 1, it is characterized in that described fluorescence sampling control signal produces circuit 25 and comprises the R-S trigger 25-1 that is made up of CO43, the 1MHz oscillator 25-2 that 2/4 CO36 forms, the level Four of being made up of four C182 cascades can preset several frequency dividers/divider 25-3, two binary counter 25-4 and 25-5 that form by CO34, compose in parallel by four C540 with or switch 25-6, that form by 1/4CH4071 or the door 25-7, the phase inverter 25-8 that CO36 forms, or the output terminal of door 25-7 connects R-S trigger 25-1 respectively, the R end of binary counter 25-4 and 25-5, the Q of binary counter 25-5 and Q output terminal connect respectively with or switch 25-6 KA at different levels and KB end, with or eight of switch 25-6 put several input ends eight output terminals corresponding and be connected with depositing display 27-2, its output terminal connects several input ends of putting of frequency divider/divider 25-3 respectively, " O " output terminal of frequency divider/divider 25-3 connects the input end of phase inverter 25-8 and the CL input end of binary counter 25-4 respectively, the output terminal of phase inverter 25-8 connects the CL end of binary counter 25-5, the S of R-S trigger 25-1 input termination governor circuit 28 with output terminal door 28-6, the input end of its Q output termination oscillator 25-2, the input end of output termination frequency divider/divider 25-3 of oscillator 25-2, the Q output terminal of binary counter 25-4 connects the control input end of linear gate 18, the input end of its Q output termination or door 25-7, or another input termination governor circuit 28 of door 25-7 put " O " output terminal.
5, a kind of laser microanalysis instrument according to claim 1, it is characterized in that described A/D converter 19 comprises 4 1/2 double integration A/D conversion logics of CH259 controller 19-11, CH3130 operational amplifier 19-1 and 19-2, C544 linear gate 19-3,19-4,19-5,19-6,19-7,19-8, the R-S trigger 19-10 that monostable circuit 19-9 that 1/2CO43 forms and 1/2CO43 form, logic controller 19-11, operational amplifier 19-1,19-2, linear gate 19-6,19-7 and 19-8 form one from steady zero integral device, two input ends of linear gate 19-3 connect the Q output terminal of the binary counter 25-4 of fluorescence signal acquisition cuicuit 17 and fluorescence sampling control signal generation circuit 25 respectively, linear gate 19-3,19-4, after linking to each other, the output terminal of 19-5 connects input end from steady zero integral device, the K2 of logic controller 19-11, K3 is connected linear gate 19-4 respectively with the K4 output terminal, the CL end of the input end of 19-5 and monostable circuit 19-9, the Q output terminal of monostable circuit 19-9 connects the input end of linear gate 19-8, its Q output terminal connects the S input end of R-S trigger 19-10 through a R-C differentiating circuit, the Q output terminal of R-S trigger 19-10 connects the input end of linear gate 19-6 and 19-7 respectively, the R input end warp-R-C differentiating circuit of R-S trigger 19-10 is connected with the output terminal with door 28-6 of governor circuit 28, and the 2Hz input end of logic controller 19-11 connects the Q output terminal of the monostalbe trigger 28-19 of governor circuit 28.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89104227 CN1015828B (en) | 1989-06-28 | 1989-06-28 | Laser microanalysis instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89104227 CN1015828B (en) | 1989-06-28 | 1989-06-28 | Laser microanalysis instrument |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048452A true CN1048452A (en) | 1991-01-09 |
| CN1015828B CN1015828B (en) | 1992-03-11 |
Family
ID=4855487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89104227 Expired CN1015828B (en) | 1989-06-28 | 1989-06-28 | Laser microanalysis instrument |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015828B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374952C (en) * | 2005-12-30 | 2008-03-12 | 中国科学院化学研究所 | Femtosecond time resolution fluorescence deficit system |
| CN106033129A (en) * | 2014-10-27 | 2016-10-19 | 韩国地质资源研究院 | Mineral search apparatus using smart device |
| CN106841153A (en) * | 2017-03-29 | 2017-06-13 | 核工业理化工程研究院 | Micro-uranium analyzer |
-
1989
- 1989-06-28 CN CN 89104227 patent/CN1015828B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374952C (en) * | 2005-12-30 | 2008-03-12 | 中国科学院化学研究所 | Femtosecond time resolution fluorescence deficit system |
| CN106033129A (en) * | 2014-10-27 | 2016-10-19 | 韩国地质资源研究院 | Mineral search apparatus using smart device |
| CN106033129B (en) * | 2014-10-27 | 2018-07-24 | 韩国地质资源研究院 | Utilize the mineral detection device of intelligent terminal |
| CN106841153A (en) * | 2017-03-29 | 2017-06-13 | 核工业理化工程研究院 | Micro-uranium analyzer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1015828B (en) | 1992-03-11 |
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