WO2020087891A1 - Water-carrying atomic fluorescence analysis device and atomic fluorescence analysis method - Google Patents

Abstract

Provided is a water-carrying atomic fluorescence analysis device and an atomic fluorescence analysis method, relating to atomic fluorescence analysis in the field of analytical chemistry, the device includes a water-carrying infusion system, a reactor assembled in the outer cover, an atomizer, an excitation light source, a detector, and the like, atomic fluorescence analysis is carried out by water-carrying and the quartz furnace outer tube sampling method. The device has a compact structure, which is convenient for assembly, operation and maintenance, the analysis method can effectively overcome the memory effect and improve the detection sensitivity and accuracy.

Description

Water-carrying current atomic fluorescence analysis device and atomic fluorescence analysis method Technical field

The invention belongs to the field of analytical chemistry, and relates to atomic fluorescence analysis, in particular to improvement of existing atomic fluorescence instruments and atomic fluorescence analysis methods.

Background technology

Atomic fluorescence analysis has been widely used in the determination of trace As, Sb, Bi, Hg, Se and other elements. The basic principle is that the ions of the element to be tested in an acidic medium (usually hydrochloric acid) interact with a strong reducing agent (usually potassium borohydride or sodium borohydride) to be reduced to a gaseous hydride (or Hg atom), while producing Hydrogen; hydride molecules dissociate into ground state atoms in a high-temperature hydrogen flame, and are excited to a high energy state by radiation of a specific frequency of the excitation light source. Due to the extremely unstable high energy level, the excited state atoms are in the form of optical radiation during deexcitation Fluorescence that emits characteristic wavelengths. The fluorescence intensity is related to the concentration of the element to be measured, and the fluorescence signal is measured by a detector (usually a photomultiplier tube) to obtain the concentration of the element to be measured.

The atomic fluorescence analysis device (also called atomic fluorometer and atomic fluorescence photometer) designed according to the above principles mainly includes infusion system, vapor generation system (or reactor), atomizer, excitation light source, detector and control system. . The infusion system is used to transport the test solution (sample solution) and the reducing agent. The test solution and the reducing agent undergo a chemical reaction in the vapor generation system to generate gaseous atoms, hydride molecules and hydrogen (called vapor). The atomizer is used to make the hydride The molecules dissociate into atoms, and the excitation light source and detector are used to excite fluorescence and collect fluorescence signals, respectively, and the detection result is obtained by calculating the value of the obtained fluorescence signal through the control system.

In the existing atomic fluorescence analysis, the reaction products generated in the reactor are led out of the inner tube of the quartz furnace in the atomizer with a small flow of carrier gas (usually Ar gas), where the hydrogen gas is ignited as a hydrogen flame, hydride Atomization in a ignited hydrogen flame. In order to ensure that there is continuous hydrogen production during the measurement process to maintain the hydrogen flame, the existing infusion system uses HCl-NaBH ₄ (KBH ₄ ) as the carrier fluid to transport the test solution, which results in the consumption of large amounts of high-purity HCl and Reducing agent, correspondingly bring long sample injection and measurement time, high furnace temperature, large memory effect, no complete signal spectrum, or often difficult to ignite the hydrogen flame, etc. A large number of acids also pollute the operating environment and corrode the instrument, etc. Disadvantages.

Summary of the invention

In order to solve the above problems, the present invention provides an atomic fluorescence analysis device.

The water-borne atomic fluorescence analysis device provided by the present invention includes an infusion system and an instrument body. The instrument body includes a housing and a reactor, an atomizer, an excitation light source, a detector, and a control system assembled in the housing. The infusion system includes:

A test solution bottle for holding the sample solution to be tested. The test solution bottle is connected to the reactor through a sample tube;

A reagent bottle for containing the reducing agent, the reagent bottle is connected to the reactor through the reagent inlet tube;

A water bottle for holding pure water. The water outlet of the water bottle is connected to the inlet of the sampling tube and the inlet of the reagent tube through two water inlet tubes, and the water inlet tube is controlled to feed water into the sample tube and the reagent inlet tube by a switch; and

The infusion system does not contain a supporting device for infusion of carrier acid.

In the above water-borne current atomic fluorescence analysis device, the sample inlet tube and the reagent inlet tube are both liquid inlet capillaries, and the water bottle is changed to two water cups, one water cup is used to hold the cleaning water, and the other water cup is used to hold the load For flowing water, the liquid inlet heads of the two liquid inlet capillaries are reinserted in two glasses of water.

In the above-mentioned water-carrying current atomic fluorescence analysis device, two liquid inlet capillaries are connected to the reactor through a peristaltic pump, and the peristaltic pump is used to control the transport speed and amount of liquid of the test liquid, reagents and carrier water in the liquid inlet capillary.

In the above water-borne atomic fluorescence analysis device, the atomizer includes a quartz furnace having an outer tube and an inner tube, the outer tube of the quartz furnace is connected to the gas outlet line of the reactor, and the inner tube of the quartz furnace is connected to argon as an auxiliary gas Gas line.

In the above water-carrying current atomic fluorescence analysis device, the atomizer includes a furnace body support, a furnace core, a quartz furnace sheathed in the furnace core, a furnace body cover sheathed outside the furnace core, a ceramic cover plate, and electric furnace wire, etc. Components, the furnace core and the outer shell of the furnace are made of insulating and heat-resistant non-metallic materials, and the components are clamped or directly assembled without screws.

In the above water-borne current atomic fluorescence analysis device, at least two clamping grooves are provided on the upper end of the outer shell of the furnace, a snap is positioned on the side of the ceramic cover plate, and the upper end of the outer shell of the furnace and the ceramic cover are locked Board connection.

In the above water-carrying current atomic fluorescence analysis device, the electric furnace wire sheath is embedded between the ceramic cover plate and the quartz furnace nozzle, and a ceramic heat insulation layer is provided between the ceramic cover plate and the top surface of the furnace core instead of Asbestos and ceramic insulation support and position the electric furnace wire at the nozzle of the quartz furnace.

In the above water-borne current atomic fluorescence analysis device, the upper part of the furnace body support is provided with a groove body and a step, and the side wall of the groove body is provided with two groove holes; the lower part of the furnace core is provided with a protrusion, and the protrusion is embedded in the Tank body; the inner tube joint and the outer tube joint of the lower part of the quartz furnace are clamped in the slot holes and protrude to the side; the quartz furnace is set in the cavity of the furnace core, and the nozzle of the quartz furnace protrudes upward from the furnace core The top surface; the outer casing of the furnace is sheathed on the periphery of the furnace core, and the bottom of the outer casing of the furnace abuts on the step of the furnace body support.

In the above water-borne atomic fluorescence analysis device, the housing further includes an open optical ring, the optical ring includes a housing, and a mounting hole is provided on one side of the housing for mounting an excitation light source and a detector, respectively. The opposite side shell on the side where the mounting hole is located is provided with a side cutting groove, which is used to transmit the light emitted by the excitation light source.

In the above water-carrying current atomic fluorescence analysis device, the size of the side cut groove matches the adjustment range of the excitation light source, so that the characteristic spectrum emitted by the excitation light source will not be irradiated onto the housing of the optical ring.

In the above water-carrying current atomic fluorescence analyzer, the inside of the housing of the atomic fluorometer facing the side cut groove of the casing is covered with light-absorbing paper coated with black light-absorbing material.

In the above water-carrying current atomic fluorescence analysis device, the housing also includes a circuit gas path integrated module, the module includes a bottom plate and a switching power supply installed on the bottom plate and a vertical frame type electrical integration unit, the vertical frame type electrical integration The unit includes a power board, a control board and a gas control board with a fixed interval in the vertical direction. The gas control board is equipped with a gas control unit and a gas pressure gauge to control the flow rate of the gas channel of the gas control unit; The supplied power is modulated into different ranges of DC power supply to control the main board and air control unit.

In the above waterborne current atomic fluorescence analysis device, the bottom plate and the bottom of the main body of the instrument are nested with slide rails and grooves to achieve displacement.

In the above water-borne current atomic fluorescence analysis device, a large display screen is provided on the front panel of the outer cover of the main body of the instrument to display the contents of the desktop system.

The water-borne current atomic fluorescence analysis device further includes a lamp tube position adjustment device, which adjusts the excitation light source in the horizontal direction and the vertical direction, and the adjustment knob is located on the side of the instrument body shell.

In the above water-carrying current atomic fluorescence analysis device, the lamp position adjusting device includes:

Lamp holder, used to install the lamp;

The support base is equipped with a lamp base on its upper surface;

The horizontal adjustment mechanism is a gear combination structure, which is used to convert the rotation of the horizontal knob into the horizontal movement of the lamp holder with the lamp installed;

Vertical adjustment mechanism, including a screw and a scissor structure connected to the screw through a screw nut assembly, used to convert the rotation of the screw into a change in the angle of the scissor structure to push the support seat supported on the scissor structure up and down Vertical movement

The fixing frame is used to support the horizontal adjustment mechanism and the vertical adjustment mechanism.

In the above water-borne current atomic fluorescence analysis device, elastic clamping pieces are fixed on both sides of the lamp holder respectively, the lower ends of the two clamping pieces are fixed on the sides of the lamp holder, the upper ends are bent outward, and the two clamps The tight piece forms an upper narrow opening with a narrow upper and lower accommodating space, which is used for installing a lamp tube.

In the above water-borne current atomic fluorescence analysis device, the level adjustment mechanism includes:

The rack is fixed to the bottom of the lamp holder;

Straight gear, equipped with integrated sleeve, and meshed with the rack;

The lower end of the straight rack adjustment shaft is rotatably mounted on a support beam. The two ends of the support beam are fixed on the fixing frame. ;

Two vertically arranged and meshed bevel gears, the horizontal bevel gear is fixed on the straight gear adjustment shaft, and the vertical bevel gear is fixed on the end of the bevel gear adjustment shaft;

The horizontal knob is connected to the bevel gear adjusting shaft through a coupling.

In the above water-borne current atomic fluorescence analysis device, the support base includes a horizontal plate and first side plates disposed vertically on both sides of the horizontal plate, and the spur gear is fixed in a groove opened at the bottom of the lamp base, and the bottom groove of the lamp base A sliding sleeve is fixed on both sides of the sliding sleeve, and the sliding sleeve can be slidably inserted into a third sliding slot opened on the horizontal plate.

In the above water-borne current atomic fluorescence analysis device, the fixing frame includes a base, support plates fixed at both ends of the base, and second side plates provided on both sides of the base. The second side plate is provided with mounting holes and a first chute , To support the vertical adjustment mechanism.

In the above water-borne current atomic fluorescence analysis device, the vertical adjustment mechanism includes:

The scissor structure formed by the two support links, the left two corners of the scissor structure are each provided with fixing rods, and the two right corners are respectively provided with sliding rods. The mounting holes of the two side plates and the first side plate are fixed; both ends of the sliding rod are slidably sleeved in the second slide groove of the second side plate and the first slide groove of the first side plate;

The screw and the screw nut assembly threaded on the screw and connected to the screw, the head of the screw passes through the bearing, the support plate, the screw nut assembly and is fixed in the left bearing, the tail of the screw passes a coupling It is connected to the vertical knob, and the upper end of the scissor structure formed by the two support links bears against the horizontal plate of the support base, and a sliding rod in the scissor structure passes through the screw nut and can slide through the second side plate. In the second chute.

The present invention also provides an atomic fluorescence analysis method using any of the above-mentioned water-borne current atomic fluorescence analysis devices, including using the infusion system to carry water after sampling and sampling from the outer tube of the quartz furnace using water as a current-carrying and atomization process Until the detection process is completed.

In the above-mentioned atomic fluorescence analysis method, the outer tube sampling means that the mixed gas of mercury atoms or hydride and hydrogen carried by the carrier gas from the reactor is passed into the outer tube of the quartz furnace, and the auxiliary gas (Ar gas) is introduced Lead into the inner tube of the quartz furnace and control the flow of carrier gas and auxiliary gas.

In the above atomic fluorescence analysis method, the flow rate of the carrier gas (Ar gas) carrying the mixed gas to the outer tube is increased to 1000-1200ml / min, and the flow rate of the auxiliary gas (Ar gas) to the inner tube is reduced to 400-600ml / min or without auxiliary gas (ie, the flow rate is 0ml / min).

In the above atomic fluorescence analysis method, the flow rate of the mixed gas passed into the outer tube of the quartz furnace is controlled to be uniform.

In the above atomic fluorescence analysis method, the sampling refers to simultaneously introducing a test solution of a certain acidity (hydrochloric acid concentration range of 4% -10%) and a reagent of a certain concentration, and the water as a carrier current means that pure water is used as a carrier The flow carries the test solution and reagent into the reactor.

In the above atomic fluorescence analysis method, the sampling time is 4-5 seconds, and the time from the water carrier flow to the end of the measurement is 8-10 seconds.

In the above-mentioned atomic fluorescence analysis method, two water cups are used to contain pure water, and after sampling, the inlet end of the inlet capillary that transports the test solution and reagents is inserted between the two glasses of water, sampling / delay / insert / measurement time Respectively 4-5 / 0 / 2-3 / 8-10 seconds, that is, sampling time 4-5 seconds, delay time is zero seconds, replacement time is 2-3 seconds, current carrying to the end of the measurement time is 8-10 second.

In the above atomic fluorescence analysis method, the atomization process further includes a process of controlling the intermittent ignition of the hydrogen flame, and the light source and the detector are excited during the combustion time of the hydrogen flame.

With the above solution, the device of the present invention is highly integrated and compact in structure, which is convenient for assembly, adjustment, operation and maintenance. The analysis method of the present invention uses water as a carrier current to perform atomic fluorescence analysis, which breaks through the traditional atomic fluorescence analysis using an acid medium (usually hydrochloric acid) With the strong reducing agent (usually potassium borohydride or sodium borohydride) as a current-carrying constraint, it can effectively overcome the memory effect and improve the measurement sensitivity and accuracy. It is a new generation of atomic fluorescence analysis technology.

The present invention will be described in detail below with reference to the drawings and embodiments.

BRIEF DESCRIPTION

FIG. 1A is a schematic diagram of the overall appearance of the water-borne current atomic fluorescence analysis device of the present invention;

1B is a schematic diagram of the decomposition structure of the water-carrying current atomic fluorescence analysis device of the present invention;

2A is a schematic diagram of the composition of the infusion system in the atomic fluorescence analyzer of the present invention;

2B is a schematic diagram of the simplified infusion system composition and liquid infusion in the atomic fluorescence analyzer of the present invention;

3A is a schematic diagram of the decomposition structure of the atomizer in the atomic fluorescence analyzer of the present invention;

3B is a longitudinal cross-sectional view of an atomizer in an atomic fluorescence analysis device of the present invention;

3C is a schematic view of the appearance of the atomizer in the atomic fluorescence analysis device of the present invention;

3D is a schematic diagram of the sampling method of the outer tube of the quartz furnace of the present invention in atomic fluorescence analysis;

3E is a schematic diagram of the sampling method of the inner tube of the quartz furnace in the existing atomic fluorescence analysis;

Figure 4-1 is a perspective structural view of a lamp tube position adjusting device in an atomic fluorescence analysis device of the present invention;

4-2 is an exploded schematic view of the lamp tube position adjusting device in the atomic fluorescence analyzer of the present invention;

4-3 is a schematic structural view of the level adjustment mechanism in the atomic fluorescence analyzer of the present invention;

4-4 is a schematic structural view of the vertical adjustment mechanism in the atomic fluorescence analyzer of the present invention;

4-5 is a longitudinal cross-sectional view of the lamp tube position adjusting device in the atomic fluorescence analysis device of the present invention;

4-6 are schematic diagrams of cooperation between a lamp tube position adjusting device and a lamp tube in the atomic fluorescence analysis device of the present invention;

4-7 is a schematic diagram of the state of the horizontal adjustment mechanism when the lamp holder in the atomic fluorescence analyzer of the present invention is at the highest position;

Figure 5-1 is a front view of an optical circle installed in the atomic fluorescence analysis device of the present invention;

5-2 is a plan view of the optical circle in the atomic fluorescence analyzer of the present invention;

5-3 is a perspective view of the optical ring in the atomic fluorescence analyzer of the present invention;

5-4 is a rear view of the optical circle of the atomic fluorescence analyzer of the present invention;

5-5 is a left side view of the optical circle in the atomic fluorescence analyzer of the present invention;

6-1 is a schematic structural diagram of an integrated circuit gas circuit module in the atomic fluorescence analysis device of the present invention;

Figure 6-2 is a schematic structural view of the vertical frame in the integrated circuit gas circuit module of Figure 6-1;

6-3 is a schematic diagram of the circuit gas circuit integrated module shown in FIG. 6-1 assembled in the atomic fluorescence analysis device of the present invention;

6-4 is a control principle diagram of the atomic fluorescence analyzer of the present invention;

FIG. 7A is the peak curve (fluorescence value-time) of Cd measured in Detection Example 1;

7B is a standard curve (fluorescence value-concentration) for measuring Cd in detection example 1;

FIG. 8A is the peak curve (fluorescence value-time) of Hg / As measured simultaneously in detection example 2;

FIG. 8B is the standard curve (fluorescence value-concentration) of Hg and As in the Hg / As mixed solution simultaneously measured in Example 2.

FIG. 9A is the peak curve (fluorescence value-time) of Pb measured in Detection Example 3;

FIG. 9B is a standard curve (fluorescence value-concentration) of Pb in detection example 3. FIG.

detailed description

The invention changes the sampling method of the infusion system and the sampling method of the atomizer quartz furnace on the basis of the original atomic fluorescence instrument, and improves and adjusts various components from assembly, adjustment, automatic control and other aspects, and proposes a breakthrough tradition A new type of atomic fluorescence device bound by concepts, and supporting the formation of new atomic fluorescence detection technology.

Similar to the traditional atomic fluorometer, the atomic fluorescence analysis device of the present invention mainly includes a transfusion system, a vapor generation system (or reactor), an atomizer, an excitation light source, a detector, and a control system. The functions and functions of each part are The original atomic fluorometer is the same, but the following special designs and unique combinations are proposed in the present invention, including:

A. Abolish HCL-NaBH ₄ as the current-carrying liquid inlet method, and use pure water as the current-carrying liquid;

B. The sampling method of the quartz furnace in the atomizer adopts the outer tube sampling technology;

C. Intermittent heating of the furnace wire;

D. Use a new non-metallic furnace body;

E. Use open optical circle;

F. Go to peripheral equipment, integrated assembly;

G. Abolish the asbestos pad of the insulating layer of the quartz furnace tube mouth, and use mica, ceramics, etc. as the insulating layer;

H. Adopt fast sampling method and matching testing procedures; a quick desktop system integrating measurement, display, printing and storage;

I. Adopt the lamp tube position adjustment mechanism to quickly adjust the lamp tube position device and angle;

J. Using current limiting technology to allow ground state atoms or hydrides and hydrogen to pass to the quartz furnace at a relatively uniform speed.

The following describes each part of the atomic fluorescence analyzer of the present invention in combination with the above features.

Infusion system

The characteristic A of the present invention is that the HCL-NaBH ₄ is eliminated as a current-carrying method during the liquid feeding process, and pure water is used as the current-carrying method. The infusion system designed according to this is shown in Figure 2A, including: a test solution bottle for holding the sample solution to be tested, a reagent bottle for holding the reducing agent, and a water bottle for holding purified water. The test solution bottle passes The sampling tube communicates with the reactor, the reagent bottle communicates with the reactor through the reagent tube, the water bottle outlet communicates with the inlet of the sample tube and the inlet of the reagent tube through the water tube, and the water inlet tube is controlled by the switch Or enter the reagent tube into the water. The unique design of the infusion system is that the infusion system does not include a supporting device for infusion of hydrochloric acid, which is significantly different from the known infusion system.

As an example, a simplified infusion system is shown in FIG. 2B, including: a test solution bottle for containing the sample solution to be tested and a reagent bottle for containing the reducing agent. The test solution bottle and the reagent bottle respectively react with the reaction through the inlet capillary Two water bottles for holding pure water, namely water cup 1 and water cup 2, water cup 1 contains cleaning water to clean the two inlet capillaries, water cup 2 contains carrier water as carrier current. The peristaltic pump can be used in the infusion process of atomic fluorescence analysis. After the test solution and reagents are input into the sample storage ring (called "sampling") by the two feed capillaries under the action of the peristaltic pump, the head of the two feed capillaries (free End) into the clean pure water of the water cup 1 (see the dashed line in FIG. 2B), and then the tip of the two inlet capillaries are then transferred into the water cup 2 (see the dotted line in FIG. 2B, called the "change plug "), The test solution and reagents in the sample loop are carried to the reactor with the current-carrying purified water.

Using this simplified infusion system, after the test solution and reagents are delivered, immediately place the heads of the two inlet capillaries in the water cup 1 to clean the solution that may be contaminated on the outer wall, and then place it in the water cup 2 to take the good solution with water. Until the end of the measurement. The specific operation can be:

A1) Sampling: Insert the sampling heads of the two inlet capillaries into the test solution (blank solution, standard solution or sample solution) and the reagent (NaBH ₄ ) solution for sampling. After 4-5 seconds, the peristaltic pump stops working;

A2) Replacing: Take the two liquid inlet capillary heads out of the washing water in the water cup 1 and wash it, then transfer it into the water-carrying water of the water cup 2 and restart the peristaltic pump;

A3) Carrier current measurement: Carrier water carries test solution and reagent into the reactor, and the instrument immediately measures the fluorescence signal of the test solution.

In this operation, the sampling / delay / replacement / measurement time is 4-5 / 0 / 2-3 / 8-10 seconds, that is, A1) the sampling time is 4-5 seconds, the delay is zero seconds, A2) The replacement insertion time is 2-3 seconds, and A3) current-carrying measurement time is 8-10 seconds.

The invention uses the infusion system to creatively use water as a carrier current in atomic fluorescence analysis, ending the detection method that used HCl and NaBH ₄ as a carrier current for more than 30 years, and can detect trace or trace As, Sb, The detection of Bi, Pb, Se, Cd and Hg shows that the infusion technique using water instead of HCl and reducing agent as the carrier current can be used in atomic fluorescence analysis, and its beneficial effects are: unlike HCl and NaBH ₄ as the carrier current, pure water It does not contain the component to be measured, and there will not be any chemical reaction with the test solution or reducing agent during the infusion carrier flow process, and there will be no large amount of bubbles (caused by the hydrogen generated by the acid and reducing agent) adhering to the wall of the flow path. Make all infusion channels flushed most thoroughly. Therefore, the atomic fluorescence analysis using water as the carrier current effectively overcomes the memory effect, improves the measurement sensitivity and accuracy, and saves a large amount of high-purity HCl and reducing agent NaBH _{4. The} analysis cost is greatly reduced and the operating environment is also obtained. Significantly improved.

Atomizer

The feature D of the present invention uses a new non-metallic furnace body, the feature G is abandoning the asbestos pad and uses a ceramic insulation layer, the feature B is a quartz furnace using an outer tube sampling technology, the feature J is a current limiting technology, and the feature C is a pair of furnaces The filaments are heated intermittently, and these features are reflected in the improvement and use of the atomizer.

Features D and G refer to the new atomizer 30 designed by the present invention. For its appearance and structure, see FIG. 1B and FIG. 3C, and for its structure and structure, refer to FIGS. 3A and 3B, including: furnace core 31, quartz set in furnace core 31 Furnace 33, furnace body cover 32 fitted outside the furnace core 31, ceramic cover plate 34 clamped to the upper end of the furnace body cover, electric furnace wire 37 embedded between the ceramic cover plate 34 and the nozzle of the quartz furnace 33, and filled in The ceramic heat insulation layer 36 between the ceramic cover plate 34 and the top surface of the furnace core 31 constitutes the furnace body part, and a furnace body support 35 is provided at the bottom of the furnace body for supporting the furnace body. Here: The quartz furnace 33 is an existing commercially available product, which is a sleeve composed of a center tube (inner tube) and an outer tube separated from each other. The inner tube and the outer tube are provided with an inner tube connector 331 and an outer tube connector 332, respectively. The furnace core 31 is an I-shaped cavity member as a whole. A quartz furnace 33 is enclosed in the cavity. The nozzle 333 of the quartz furnace extends upward from the top surface 313 of the furnace core 31. The shape and size of the lower protrusion 311 of the furnace core 31 and the furnace body support The upper groove 351 of the seat 35 is matched, and the protrusion 311 is embedded in the groove 351. An inner groove 312 may be formed in the upper part of the furnace core 31 to accommodate the ceramic heat insulation layer 36. Two grooves 352 are defined in the side wall of the upper groove 351 of the furnace body support 35, and the inner pipe joint 331 and the outer pipe joint 332 of the quartz furnace 33 extend laterally through the groove 352. The outer casing 32 of the furnace is cylindrical, and is sleeved around the outer periphery of the furnace core 31. The bottom 321 abuts the step 353 of the furnace body support. The upper portion is provided with at least two clamping grooves 322, and the buckle 342 is provided on the side of the ceramic cover 34 Card-locking. The electric furnace wire 37 is sheathed and installed on the inner side of the ceramic cover plate 34, and is supported and fixed around the nozzle 333 of the quartz furnace 33 by the ceramic insulation layer 36 filled between the ceramic cover plate 34 and the top surface of the furnace core 31. The shape of the ceramic heat-insulating layer 36 changes with the shape of the filled voids, and one or more kinds of heat-insulating material combinations (without asbestos materials) such as ceramic sheets, ceramic fibers, mica sheets can be selected, as shown in FIG. 3B, ceramic fiber rope 363, mica The ceramic insulating layer composed of the sheets 362 and the ceramic sheets 361 is sequentially stacked, wherein the ceramic fiber rope 363 is embedded in the inner groove 312 formed in the upper part of the furnace core 31.

The above components are assembled in the following way: the upper part of the quartz furnace 33 is sleeved into the inner cavity of the furnace core 31 from the bottom up, the furnace core 31 and the bottom of the quartz furnace 33 are sleeved into the upper tank 351 of the furnace body support, and the inner tube of the quartz furnace 33 The connector 331 and the outer tube connector 332 are snapped into the slot 352; the ceramic cover plate 34 with the electric furnace wire 37 installed is snapped onto the upper end of the furnace body cover 32, and the ceramic insulation layer is filled from the upper end of the furnace core 31 to the nozzle port of the quartz furnace 32 36. Finally, the outer casing 32 of the furnace is sheathed outside the furnace core 31 and abuts on the step 353 of the furnace body support 35. After the assembly is completed, the atomizer is obtained. The assembly uses a slot and other structures to achieve the fixation between the components, without screws, and the installation is simple, which is convenient for maintenance and replacement.

In this atomizer, the furnace core 31 and the furnace body cover 32 are processed with insulating and heat-resistant non-metallic materials, and no metal materials are used. The furnace body is made of non-metallic materials with excellent heat dissipation performance and complete insulation. It can be repaired without cooling after stopping work, and the temperature of the furnace body will not be too high during the work process to overcome the phenomenon of baseline drift, and the device has good working stability; The parts are matched and assembled, no screw fastening is required for installation, and they can be disassembled and repaired as a whole; the quartz furnace tube mouth uses mica, ceramics and other thermal insulation materials, discards the carcinogen asbestos, and overall improves the quality of the atomizer.

In terms of using an atomizer, feature D relates to a pioneering outer tube sampling method proposed by the present invention, and feature J further uses a current limiting technology in combination. As shown in Figure 3D and compared with Figure 3E, the original atomic fluorescence analysis uses 300-400ml / min carrier gas (Ar gas) to carry the reaction product Hg atoms or hydride and hydrogen from the inner tube of the quartz furnace, outside the quartz furnace The tube is filled with 900-1100ml / minAr as shielding gas, as shown in Figure 3E. In the present invention, the hydride and hydrogen mixed gas carried by the carrier gas (such as argon) is reconnected to the outer tube, and the argon gas originally used as the shielding gas is reconnected to the inner tube as auxiliary gas, as shown in FIG. 3D , This is the outer tube injection. On the other hand, increase the flow rate of the carrier gas (Ar gas of the outer tube of the device) with the mixed gas to 1000-1200ml / min so that the hydrogen in the outer tube of the quartz furnace is ignited to form a larger hydrogen flame. The flow rate of the auxiliary gas (Ar gas in the inner tube of the device) is reduced to 400-600ml / min. The auxiliary gas flow rate of the inner tube is small, which only pushes up the hydrogen flame, and even detects certain elements (such as Cd). At this time, the inner tube is not even vented with auxiliary Ar gas (ie 0ml / min). At the same time, the flow-limiting technology is used to control the delivery speed of the reaction gas, that is, the flow rate of the mixed gas into the outer tube of the quartz furnace is controlled, so that the ground state atoms or hydrides and hydrogen carried by the Ar gas carrier enter the quartz at a relatively uniform flow rate The outer tube of the furnace, so that a stable hydrogen flame can be obtained.

The outer tube sampling method changes the mode of introducing hydride (or Hg atom) and hydrogen from the inner tube in atomic fluorescence analysis. The sampling mechanism of the outer tube is: gaseous atoms or molecules and hydrogen generated by the chemical reduction reaction are introduced from the outer tube of the quartz furnace with the carrier gas (Ar gas) carrier tape, and the hydride (or mercury atom) of the element to be tested is mixed with hydrogen The gas rises along the inner wall of the outer tube of the quartz furnace, the hydrogen gas is ignited by heat at the mouth of the quartz furnace tube immediately, and the hydride is dissociated under the high temperature of the hydrogen flame in the Ar gas atmosphere. The auxiliary gas (usually argon) entering the inner tube pushes the hydrogen flame upward, and the formed hydrogen flame is much larger than the inner tube injection (compare Figure 3D and Figure 3E). The outer tube sampling technology makes the hydrogen heated by the furnace wire located at the outer tube nozzle. The hydrogen flame is easy to ignite, and the formed hydrogen flame has a large and stable shape, a large luminous solid angle, and a significantly improved measurement sensitivity. For elements that produce less hydrogen in the reaction, such as Pb and Sn, the outer tube sampling method makes the hydrogen closer to the furnace wire heated at the quartz furnace port, and the hydrogen flame is easily ignited. The flame cannot be ignited basically, and it is very difficult to determine these elements. It can be seen that the present invention also solves the problem of atomic fluorescence detection of elements that generate less hydrogen in the reaction.

Feature C involves a change in the heating method of the furnace wire, changing the method of keeping the hydrogen flame uninterrupted during the original analysis to intermittent heating. In intermittent heating, the hydrogen flame is only ignited for a period of time when measuring the signal, about half The furnace is in the cooling period, so the phenomenon of baseline drift caused by the increase of furnace temperature in atomic fluorescence analysis is overcome.

Lamp position adjusting device

The feature I of the present invention is the rapid adjustment of the position of the lamp tube. The vertical and horizontal positions of the emission light source (hollow cathode lamp) can be quickly adjusted with the two knobs outside the case. This feature is realized by the specially designed lamp tube position adjusting device 60 (see FIG. 1B) of the present invention. In view of the problems of inconvenient operation and difficulty in ensuring the position of the lamp tube by the existing lamp tube position adjustment device, the present invention proposes a lamp tube position adjustment device that is easy to operate and can be continuously adjusted. The position adjustment device uses a gear The combined structure converts the rotation of the horizontal knob into the horizontal movement of the lamp holder with the lamp installed, and uses a screw and a scissor structure connected to the screw to convert the rotation of the screw into a change in the angle of the scissor structure. Thereby, the support base supported on the scissor structure is moved vertically.

The structure of the lamp tube position adjustment device is shown in Figure 4-1 to Figure 4-7, the reference numbers in the figure are:

01: lamp holder, 011: sliding sleeve;

02: fixing frame, 021: base, 022: support plate, 023: second side plate, 0231: second chute;

03: support base, 031: horizontal plate, 0311: third chute; 032: first side plate, 0321: first chute;

04: horizontal adjustment mechanism, 041: rack, 042: spur gear, 043: spur gear adjustment pump, 044: bevel gear, 045: bevel gear adjustment shaft, 046: support beam, 047: horizontal knob;

05: Vertical adjustment mechanism, 050: Scissor structure, 051: Supporting connecting rod, 052: Fixing rod, 053: Sliding rod, 054: Screw, 055: Screw nut assembly, 0551: Screw nut, 0552: Sleeve , 056: vertical knob;

06: clamping piece;

07: Lamp.

Referring to FIGS. 4-1 and 4-5, the lamp position adjusting device is used to install the lamp 07 as an excitation light source and adjust its position so that the excitation spectrum emitted by the lamp 07 irradiates the flame ignited at the exit of the atomizer. The lamp position adjusting device includes a horizontal adjusting mechanism 04, a vertical adjusting mechanism 05, a support base 03, a lamp base 01, and a fixing frame 02 for supporting the horizontal adjusting mechanism 04 and the vertical adjusting mechanism 05, and the lamp tube 07 passes through the clamping piece 06 is fixed on the lamp base 01 (see FIG. 4-6), the lamp base 01 is installed on the support base 03, and the horizontal adjustment mechanism 04 adopts a gear combination structure to convert the rotation of the horizontal knob 047 into a lamp with the lamp 07 installed The horizontal movement of the tube base 01, the vertical adjustment mechanism 05 adopts a screw 054 and a scissor structure connected to the screw through a screw nut assembly 055, which converts the rotation of the screw 054 into a change in the angle of the scissor structure, thereby pushing The support base 03 supported on the scissor structure vertically moves up and down.

As shown in Figure 4-1, the lamp base 01 is a block-shaped structure, and an arc-shaped groove is provided on the upper end for accommodating the lamp 07. The lamp base 01 is located on both sides of the arc-shaped groove and is respectively fixed and elastic Clamping piece 06, the lower end of the clamping piece 06 is fixed to the side of the lamp holder 01, the upper ends of the two clamping pieces are bent outward, and the two clamping pieces 06 form an upper narrow opening and a lower wide receiving space . During installation, press down the lamp tube 07 from the opening of the arc-shaped accommodating space, the clamping piece 06 expands outwards due to elasticity, and when the bottom of the lamp tube 07 contacts the arc-shaped groove of the lamp base 01, the clip The tension piece 06 rebounds to clamp the lamp tube 07, thereby fixing the lamp tube 07.

4-2, 4-3, and 4-5, the horizontal adjustment mechanism 04 includes a rack 041 fixed to the bottom of the lamp base 01, a spur gear 042 that meshes with the rack 041, and a spur gear 042 used for fitting Spur gear adjusting shaft 043, bevel gear 044 fixed on the spur gear adjusting shaft 043 and bevel gear 044 fixed on the bevel gear adjusting shaft 045, wherein the two bevel gears 044 are set vertically and meshed; the spur gear 042 is set There is an integrated sleeve, the sleeve is sleeved on the upper part of the spur gear adjustment shaft 043 and is connected with a plane fit. On the beam 046, both ends of the support beam 046 are fixed on the fixing frame 02; the bevel gear adjusting shaft 045 is connected to the horizontal knob 047 through a coupling. The bevel gear 044 can drive the rotation movement of the bevel gear adjusting shaft 045 through the bevel gear 044 to drive the spur gear adjusting shaft 043 and the spur gear 042 to rotate, thereby driving the rack 041 meshing with the spur gear 042 and the lamp fixed with the rack 041 The tube base 01 moves horizontally, so as to achieve the horizontal movement of the lamp tube 07 fixed on the lamp tube base 01 by the clamping piece 06.

As shown in FIG. 4-2, the support base 03 includes a horizontal plate 031 and a first side plate 032 disposed vertically on both sides of the horizontal plate 031. The horizontal plate 031 is provided with a through hole for penetrating the straight gear adjustment shaft 043 ( (See Figure 4-5), a third slide slot 0311 is provided on both sides of the through hole; the bottom of the lamp base 01 is provided with a slot for accommodating the rack 041 and the spur gear 042, the spur gear 042 is fixed to the lamp base 01 In the slot, the spur gear 042 meshes with the rack 041, and at the same time, a sliding sleeve 011 is fixed on both sides of the bottom slot of the lamp holder 01, the sliding sleeve 011 can be slidably inserted into the third sliding slot 0311, and the spur gear 042 rotates At this time, the lamp base 01 fixed with the rack 041 can be driven to move, and the sliding sleeve 011 slides in the third sliding groove 0311.

As shown in FIG. 4-2, the fixing frame 02 serves as a support mechanism for the lamp tube position adjusting device, and includes a base 021, support plates 022 fixed at both ends of the base, and second side plates 024 provided on both sides of the base. The 024 is provided with a mounting hole and a first chute 0321.

4-2, 4-4, and 4-5, the vertical adjustment mechanism 05 includes a scissor structure 050 formed by two support links 051, and two left corners of the scissor structure are each provided with fixing rods 052, two right corners are respectively provided with sliding rods 053, and both ends of the fixing rod 052 are respectively fixed through the mounting holes of the second side plate 024 of the fixing frame 02 and the first side plate 032 of the support base 03, and slide Both ends of the rod 053 are slidably inserted into the second slide groove 0241 of the second side plate 024 and the first slide groove 0321 of the first side plate 032; the vertical adjustment mechanism 05 further includes a screw 054 and a sleeve A screw nut assembly 055 connected to and screwed on the screw 054. The screw nut assembly 055 includes a screw nut 0551 and a sleeve 0552 connected to the screw nut. The head of the screw 054 passes through the right bearing, The support plate 022 and the sleeve of the screw nut assembly 055 are fixed in the left bearing. The tail of the screw 054 is connected to the vertical knob 056 through a coupling. The upper end of the scissor structure formed by the two support links 051 bears against the support seat 03 The horizontal plate 031, and a sliding rod 053 in the scissor structure passes through the screw nut 056 and can be slidably put on the first The second side 024 of the chute. When the vertical knob 056 is turned, the vertical knob 056 drives the screw 054 to rotate, which in turn drives the screw nut assembly 055 to move along the screw, so that the horizontal angle of the scissor structure becomes larger or smaller, and the upper end of the scissor structure 050 will support the seat 03 up or down, at the same time, the slide rod 053 moves in the corresponding chute.

The lamp tube position adjusting device assembled by the above components according to the above connection relationship has the following characteristics:

(1) The device adopts a gear combination structure, and through the bevel gear 044, the rotation of the bevel gear adjustment shaft 045 is converted into the horizontal rotation of the spur gear adjustment shaft 043 and the spur gear 042, and then the rack 041 meshing with the spur gear 042 drives the installation The lamp base 01 with the lamp 07 moves horizontally.

(2) In the vertical adjustment mechanism 05 of the device, the scissor structure composed of two support links 051 is connected to the screw 054 through the screw nut assembly 055, the screw 054 is threadedly connected to the screw nut assembly 055, and the screw 054 is connected to The relative movement of the screw nut assembly 055 drives the angle change of the scissor structure 050 of the two support links 051, thereby driving the support base 03 and the lamp base 01 supported on the upper end of the scissor structure to move vertically, and at the same time, the straight gear 042 moves along the straight gear The upper part of the adjustment shaft 043 moves up and down.

(3) The vertical adjustment mechanism 05 and the horizontal adjustment mechanism 04 are supported on the fixing frame 02, and the two are spatially arranged crosswise without interference. The vertical adjustment mechanism 05 passes through the fixing rod provided at the left corner of the scissor structure 052 is respectively connected to the second side plate 024 of the fixing frame 02 and the first side plate 032 of the supporting base 03, and is respectively connected to the second side plate 024 of the fixing frame 02 and the support through a sliding rod 053 provided on the right side of the scissor structure 050 The sliding groove on the first side plate 032 of the base 03 is slidingly connected; the horizontal knob 047 and the vertical knob 056 of the device are both arranged outside the shell of the atomic fluorometer, with a compact structure, convenient position adjustment, and continuous adjustment.

(4) The lamp tube 07 is fixed by the two clamping pieces 06 fixed on the lamp holder 01, and the lamp tube 07 is inserted into the upper narrow and lower arc-shaped accommodating space formed by the two clamping pieces 06. The elasticity of the clamping piece 06 clamps and fixes the lamp tube 07, and the lamp tube 07 can be automatically clamped and fixed by simply pressing the lamp tube 07 into the clamping piece to form an arc-shaped accommodating space without additional operations.

Optical circle

The feature E of the present invention is the design of an open optical ring 10 (see FIG. 1B), which removes the radiation of the excitation light source (hollow cathode lamp) out of the furnace, which can effectively reduce the influence of diffuse reflected light on the fluorescence detection, and at the same time make the furnace body installation and Maintenance is more convenient. An atomizer is installed at the lower opening of the optical ring. The atomizer outlet is located in the optical ring. A mounting hole for mounting the excitation light source and the detector is provided on one side of the housing of the optical ring. The emitted characteristic spectrum is irradiated to the inside of the housing of the atomic fluorometer separated by one end through the side-cut groove, so that no light enters the detector, thereby reducing optical interference, and simplifying the structure and facilitating installation and maintenance.

For the installation and structure of the optical ring, see Figure 5-1 to Figure 5-5. The reference signs in the figure are expressed as:

50: chimney, 30: atomizer;

10: optical ring, 101: housing, 102: upper opening, 103: lower opening, 104: side slot, 105: first mounting hole, 106: second mounting hole, 107: third mounting hole;

20: The first excitation light source;

20 ’: second excitation light source;

40: Detector.

As shown in FIGS. 5-3 to 5-5, the optical ring 10 includes a housing 101, which is a cylindrical structure, and the upper opening 102 and the lower opening 103 of the housing 101 are used to install the chimney 50 and the atomizer, respectively 30. Three mounting holes are provided in sequence on the same horizontal plane on the side of the housing 101, that is, the first mounting hole 105, the second mounting hole 106, and the third mounting hole 107, which are used to mount the first excitation light source 20, the detector 40, and the The second excitation light source 20 '(see FIG. 5-2), a side cutout 104 is formed on the opposite side of the casing 101 on the side where the mounting hole is located, and the size of the side cutout 104 is the same as that of the first excitation light source 20 and the second excitation The adjustment range of the light source 20 'is matched, so that the characteristic spectrum emitted by the excitation light source can be irradiated to the inside of the housing of the atomic fluorometer through the side-cut groove 104, but not to the housing 101.

During installation, the atomizer 30 extends into the housing 101 of the optical ring 10, and the characteristic spectra emitted by the first excitation light source 20 and the second excitation light source 20 'are directly at the center of the flame ignited by the exit of the atomizer 30, the detector 40 The optical path entrance is located at the same horizontal plane in the center of the flame, and the emission ports of the first excitation light source 20 and the second excitation light source 20 'and the optical path entrance of the detector 40 face the side cut groove 104 of the optical ring 10, and the side cut groove 104 faces the The inside of the front cover 71 (see FIG. 1B) (for example, the rear side of the display screen 74). Preferably, a light absorption paper coated with a black light absorption material is provided on the opposite side of the housing on the side where the side cut groove 104 of the optical ring 10 is located, and the light absorption paper may be directly attached to the inside of the housing of the atomic fluorescence instrument, for example, the rear side of the display screen.

During operation, the characteristic spectrum emitted by the first excitation light source 20 and the second excitation light source 20 'is directly irradiated to the rear side of the display screen at a distance from the optical circle 10 through the side cut-out groove 104 of the optical circle 10, and the light hardly enters the detector 40 light path entrance, will not form stray light. After laying the light-absorbing paper on the back side of the display screen, most of the light is absorbed to avoid reflection, thereby reducing the optical background.

The optical circle 10 designed by the invention is provided with a side cut groove 104 on the opposite side of the excitation light source emission port and the optical path entrance of the detector 40, so that the characteristic spectrum emitted by the excitation light source is irradiated to the inside of the shell of the atomic fluorometer through the side cut groove 104, stray light. Does not enter the detector, reduces optical noise, and avoids light diffusion affecting the detection results; by opening a side cut 104 on the side of the optical ring 10, the emitter mirror for removing stray light is omitted, and the structure is simplified , And maintenance can be carried out without dismantling.

Circuit pneumatic integrated module and control system

Feature F is the peripheral device of the atomic fluorescence analysis device of the present invention. Each component adopts the form of a module, which can realize assembly assembly. Feature H adopts the rapid sampling method and its matching detection program. It integrates measurement, display, printing and storage as Integrated quick desktop system; the instrument is not only neat in appearance, reasonable and compact in internal configuration, small in size, but also adopts advanced electrical control system, with a large display screen 74 (see Figure 1B) and a simple and clear desktop system, sampling and The measurement time is less than 20 seconds, and can be carried to the scene for emergency detection.

The integrated circuit gas circuit module 80 of the present invention (see FIG. 1B and FIG. 6-1) is mainly aimed at the problems of inconvenient installation and maintenance caused by the horizontal arrangement of the circuit gas circuit in the original atomic fluorometer, rapid disassembly and assembly, and large space occupation. Designed, the system sets the power board, the control board and the air control unit at intervals in the vertical space through the isolation column to form a vertical frame-type electrical integrated unit, and then fixed together with the switching power supply on a bottom plate to become an integrated structure, which saves It saves space and is convenient for disassembly and maintenance.

The configuration of the circuit gas path integrated module 80 is shown in FIGS. 6-1 to 6-3. The reference signs in the figure are expressed as:

810: vertical frame-type electrical integrated unit, 811: power board, 812: control board, 813: gas control board; 82: gas pressure gauge; 83: gas control unit, 831: proportional solenoid valve, 832: flow sensor; 84: Isolation column; 70: chassis; 86: switching power supply; 87: bottom plate; 08: pulse constant current source.

Refer to the integrated circuit pneumatic circuit module shown in FIGS. 6-1 to 6-3. The integrated circuit pneumatic circuit module includes a base plate 87, a switching power supply 86 and a vertical frame-type electrical integration unit 810, and a switching power supply 86 provided on the base plate 87 The vertical frame-type electrical integration unit 810 is powered.

As shown in FIG. 6-2, the vertical frame-type electrical integration unit 810 is a vertical frame-type modular structure, including a power board 811, a control board 812 and an air control board 813 spaced from the bottom to the top in sequence, the air control board 813 is installed with The gas control unit 83 and the gas pressure gauge 82. The gas control unit 83 includes two gas channels, which are respectively used to transport the carrier gas and the auxiliary gas. The carrier gas and the auxiliary gas are generally argon, and the argon passes through the gas pressure gauge 82 through the pipeline Connected to the gas channel of the gas control unit 83, the gas pressure gauge 82 is used to control the pressure of the incoming argon gas, generally controlled at 0.3MPa, the control board 812 controls the flow of the two gas channels of the gas control unit 83; the switching power supply 86 provides The electric power is modulated by the circuit of the power board 811 into DC power of different ranges and supplied to the control main board 812 and the air control unit 83.

In the vertical frame structure of the vertical frame type electrical integration unit 810, the hierarchy is not limited to three layers, and the arrangement order between each layer and the distance between adjacent layers are not limited.

The bottom plate 87 may be fixed on the chassis 70 of the atomic fluorometer. In order to facilitate the removal and maintenance or replacement of the circuit gas circuit integrated module 80, the bottom of the chassis 70 is provided with a convex rail, and the bottom surface of the bottom plate 87 is provided with a groove matching the convex rail of the chassis 70. The bottom plate 87 can be along the chassis 70 The raised track slides in and out, easy to install and maintain.

The integrated circuit gas circuit integrated module 80 is built into the case 70 of the atomic fluorometer. The power board 811, the control board 812 and the air control board 813 form a vertical frame structure through the isolation column 84, and the switching power supply 86, the power board 811, the control board 812 and the air control The unit 83 is electrically connected by wires or flat wires. This vertical frame structure makes full use of the limited space in the chassis 70. The structure is compact and is conducive to the miniaturization of the atomic fluorometer; the push-pull structure formed by the bottom plate 87 and the bottom of the chassis 70 is easy to disassemble And maintenance.

As shown in Fig. 6-4 (the thick line indicates the gas path is connected, and the thin line indicates the electrical connection), the control system of the device of the present invention is integrated in the circuit gas path integrated module 80, mainly including the control main board 812, and the device of the present invention, The peristaltic pump 91, the air control unit 83, the lamp tube 07, the detector 40, the display screen 74, the switching power supply 74, and the printer are all electrically connected to the control main control 812, in which:

The control board 812 is integrated with peripheral circuits such as a processor (MCU), memory, and a digital-to-analog conversion module (DAC), an analog-to-digital conversion module (ADC), an interface module, and a voltage stabilizing circuit. The processor is the core of the device of the present invention and is The brain of the entire device is responsible for the management and timing control of the electrical components of each part of the device.

The switching power supply 86 is connected to the control main board 812 through a voltage stabilizing circuit to supply power to the processor (MCU) on the control main board 812 and its peripheral circuits.

The main control main board 812 controls the operation of the peristaltic pump 91, and further controls the inflow of the test liquid, the reagent, and the carrier water in the two liquid inlet capillaries (inlet tube and reagent tube) assembled in the peristaltic pump 91.

The lamp 07 is connected to the control main board 812 through a high-voltage pulse constant current source 08, and the digital-to-analog conversion module (DAC) of the control main board 812 outputs an electric pulse with a certain duty ratio and a preset amplitude as the control pulse of the pulse constant current source 08 Signal, the pulse constant current source 08 outputs 30mA-150mA electric pulse to the lamp (excitation light source) 07 under the action of the control pulse signal, so that the lamp 07 emits the excitation light of the element to be detected. At the same time, the control main board 812 controls to receive and process the fluorescent signal of the element to be detected captured by the detector 40.

As shown in Figure 6-4, the gas control unit 83 includes two gas pipelines and a proportional solenoid valve 831 and a flow sensor 832 provided on the two gas pipelines, and argon gas (carrier gas and auxiliary gas) is provided by an argon gas bottle Enter the gas pipeline and connect to the reactor 90 or quartz furnace 33 through the gas pipeline. The proportional solenoid valve 831 is set in the gas pipeline to control the on-off and flow rate of the gas pipeline. The flow sensor 832 is set at the outlet of the gas pipeline , Used to measure the gas flow in the gas pipeline. Based on the control system, the present invention can adopt a closed-loop flow control strategy, that is, by setting a proportional solenoid valve 831 and a flow sensor 832 on the gas pipeline, the control board 812 receives the gas flow measured by the flow sensor 832, and compares the measured value of the gas flow with the gas flow Set value comparison, the difference between the two is converted to the control voltage of the proportional solenoid valve 831 and then sent to the proportional solenoid valve 831 to control the gas flow. The proportional solenoid valve 831 is used for digital control. The closed-loop flow control system can provide reliable and stable The flow rate is not easily affected by factors such as gas pressure and temperature changes.

The display screen 74 is electrically connected to the control main board 812 and is used to display a desktop operating system to realize human-machine dialogue. The printer can print the detection result and the generated curve stored on the control main board 812.

The water-borne current atomic fluorescence analysis device of the present invention is assembled from components including the above systems. The appearance of the main body of the instrument (excluding the infusion system) is shown in FIG. 1A, and the exploded structure is shown in FIG. 1B. The instrument housing includes a chassis 70, a rear cover 72, an upper cover 73, and a front cover 71. A large-size display screen 74 is installed on the front cover 71, and a desktop operating system is presented through the display screen 74 to realize human-machine dialogue; The peristaltic pump 91 of the infusion system is installed near the lower part of the side plate of 70, and the argon gas delivery pipe hole 92 is provided. On the other side, a small print output device (omitted on the right side of the figure) can be installed. The horizontal knob 047 and vertical knob 056 (combined with Figure 4-1) can be easily adjusted to the horizontal or vertical position of the lamp via the external knob on the cabinet. The reactor 90 is installed in the cabinet 70 adjacent to the peristaltic pump 91. The test solution and the reagent output tube of the peristaltic pump 91 are connected to the reactor 90; a fixed frame 93 is fixed to the support frame in the cabinet 70, and the atomizer 30 Installed on the fixing frame 93, the gas outlet pipe of the reactor 90 is connected to the outer pipe joint 332 of the quartz furnace of the atomizer 30, and the inner pipe joint 331 of the quartz furnace is connected to the argon gas pipeline as auxiliary gas; The atomizer 30 is fixed outside the cabinet 70, the chimney 50 is installed above the optical ring 10 and extends outward from the corresponding gap of the upper cover 73; the integrated circuit gas circuit module 80 is installed at the bottom of the cabinet 70, the lamp position The adjusting device 60 and the excitation light source 20 (or 20 ') are mounted on the support frame in the chassis 70 and fixed (the lamp tube can be moved horizontally or vertically), and the detector 40 is fixed on the support frame in the chassis 70; Connect the wires, install the front cover 71, rear cover 72 and upper cover 73, and the main assembly of the instrument is completed. The main body of the instrument cooperates with the infusion system to form the water-carrying current atomic fluorescence analysis device of the present invention.

Atomic fluorescence analysis is carried out by using the water-borne current atomic fluorescence analysis device of the present invention. All the analysis operations are completed on the display screen 74, which can display the structure, function and use method of the desktop system.

The desktop system is divided into five pages: "Home", "Settings", "Standard Curve Making", "Sample Test" and "Instrument Performance Index Test". "Home" recommends different elemental analysis conditions, users use this as a reference, and need to prepare the required test solutions and reagents before measurement.

The determination is carried out as follows:

1. Turn on the power and select single-channel (A or B) or dual-channel (A + B) on the "Settings" page. In general, Hg / As, As / Sb, Bi / Hg can be measured by dual-channel, Se, Pb, Cd is measured with a single channel; the lamp current, negative high pressure, pump speed, Ar gas flow rate and operating time can be set in principle without modification;

2. Turn on the lamp power, preheat the hollow core cathode lamp for 5-10min, adjust the light spot of the hollow core cathode lamp during this period, this light spot corresponds to the center axis of the quartz furnace, and its height should be 8 away from the center of the lens aperture of the quartz furnace tube -10mm.

3. Open the main valve of the Ar gas cylinder, control the pressure of the primary pressure reducing valve to 0.4MPa, and the secondary pressure reducing valve to 0.3MPa;

4. After the instrument is preheated, turn on the ventilation, turn on the power of the electric furnace wire, and place the test solution, reagent and two glasses of water in the sample tray;

5. Insert the two inlet capillaries of the peristaltic pump (refer to the inlet end, the same below) into pure water, click blank on the "Standard Curve Making" page, rinse the infusion flow path twice with test water, and then insert the capillary into the blank Solution and NaBH ₄ solution, after sampling, immediately remove the capillary from the test solution and reagent solution, first placed in the first cup for rapid cleaning, and then placed in the second cup of water, at this time drive the pump to suck water into the two capillaries, The test solution and reagents are carried by water into the reactor to undergo chemical reduction reaction, and then Hg atoms or hydrides are introduced into the hydrogen flame of the atomizer, and the blank fluorescence value is recorded by the detector until the difference between the second measurement values is not more than 5 , Take the blank average value; then measure the fluorescence value of each solution in the standard sample series from low to high concentration (usually measured twice). Enter the concentration of each standard sample series in the concentration column and click the average and curve buttons below to display the slope and intercept of the standard curve and linear equation.

6. After making the standard curve, measure the sample concentration on the "Sample" page. Before measuring the test solution, the two capillaries need to be inserted into the water again, washed twice according to the running procedure, and then the fluorescence value of the blank is measured with the standard blank and the reagent blank solution and the average value is taken. Then measure the fluorescence value of each test solution one by one, and get the corresponding test solution concentration, enter the sample weight or sampling volume of the sample and the volume fraction of the preparation solution in the corresponding column, click "enter" to get the measured sample content. If the number of samples exceeds 10, continue the measurement using pages 2-4.

7. Enable the right print or store button to print or store the standard curve or sample measurement results, and the stored data can be read or saved on the computer.

8. After the measurement is completed, the flow path needs to be washed again with water 2-3 times.

9. Turn off the hollow-core cathode lamp, furnace wire power supply, Ar gas, ventilation and host power one by one and loosen the peristaltic pump clamping plate, and finally close the Ar gas cylinder valve.

According to the above operation, the effect of element atomic fluorescence analysis using the device of the present invention is illustrated by a test example. In the examples, the reagent concentration "%" is expressed as a mass percentage concentration.

Test Example 1: Analysis of Cd

Test samples: rice, soybean

Preparation of cadmium standard curve: first prepare 10ng / ml cadmium standard solution, then take this standard solution 0, 0.5, 1.0, 1.5, 2.0, 2.5ml in a 50ml plastic quantitative bottle, and add a concentration of 50 to each solution 4ml of% HCl solution and 5ml of 5% thiourea were diluted with water to the mark to obtain a standard series solution with Cd concentration of 0, 0.1, 0.2, 0.3, 0.4 and 0.5ng / ml. After shaking, the fluorescence signals of the blank and standard series solutions were measured according to the operation process to prepare a standard curve (see Figure 7B). Figure 7A shows the peak curve of Cd. In operation, both the carrier gas and the auxiliary gas use Ar gas, and the flow rate of argon gas (outer tube) as a carrier gas is controlled to 1000-1200ml / min, and the flow rate of 0ml / min is turned off as the auxiliary gas (inner tube).

Preparation and determination of test solution:

Weigh the rice flour or soybean powder sample (about 0.1-0.2g) in a 50ml plastic quantitative bottle, add 50ml of HCl 4ml, 5% thiourea 5ml, shake for 5-10min, dilute with water to Scale, according to the volume of Table 1 to prepare the sample solution. According to the operation process, the sample solution is used as the test solution to measure the fluorescence signal of the sample solution, and the concentration of Cd is obtained from the standard curve and converted into the content in the sample. See Table 1 for the measurement results of Cd in food samples.

Table 1. Test results of Cd in rice and soybean powder (ng / g)

As can be seen from the data in the table, when the concentration of HCl is 4%, the detection sample is not pre-treated, and the atomic fluorescence analysis of water-carrying current can quickly determine cadmium in rice and other foods. The measured values are almost the same, and the measured Cd content in the sample is in agreement with the recommended value.

In this measurement operation, the sample does not need to be digested, nor does it require hydrochloric acid as the carrier current, and only consumes purified water (18.2MΩ). The measurement process takes about 50% less time than the conventional method; NaBH ₄ solution only needs to be used to participate in the reaction , Saving more than 75% compared to conventional testing. The samples in Table 1 are tested from left to right, and it can be seen that the high concentration solution has no effect on the subsequent determination. It shows that the water-carrying method eliminates the memory effect.

Test Example 2: Simultaneous determination of Hg / As

Test sample: soil

Because the content of As in the soil is much higher than Hg, the existing atomic fluorometer has been unable to measure Hg and As in this sample at the same time. In this example, the device of the present invention is used to realize the simultaneous detection of Hg and As in the same sample.

Preparation of standard curve: prepare a mixed standard solution containing 500ng / ml As and 10ng / ml Hg in advance. Take this standard solution 0, 1, 2, 3, 4, 5ml in a 50ml plastic quantitative bottle, add 5ml of 5% Vc-5% thiourea solution, 10ml of 50% HCl concentration, and dilute with water to the mark to get 0 —No. 5 series standard solution, the order of Hg concentration in the standard solution is 0, 0.2, 0.4, 0.6, 0.8, 1.0 ng / ml, and the order of As concentration is 0, 10, 20, 30, 40, 50 ng / ml.

Select the dual channel mode, and measure the fluorescence signals of Hg and As in the blank and standard series solutions simultaneously according to the above operation process, and prepare the Hg and As standard curves of the mixed standard solution respectively. Fig. 8A is the peak curve of Hg / As, and Fig. 8B is the standard curve of the mixed standard solution Hg and As (the signal of the standard curve is calculated based on the spectrum area, and the blank area has been subtracted). During operation, the flow rate of Ar gas (leading to the outer tube of the quartz furnace) as a carrier gas was 1000 ml / min, and the flow rate of Ar gas (leading to the inner tube of the quartz furnace) as an auxiliary gas was 500 ml / min.

Preparation and determination of test solution: Weigh 0.1-0.2g of soil sample according to the sample weight (G), place it in a 50ml PTFE sample tube, add 50% aqua regia to boil and decompose on a water bath for 1 hour, Transfer to 50ml plastic quantitative bottle with water, add 5ml of 5% Vc-5% thiourea solution, 10ml of 50% concentration of HCl, dilute to the mark with water, shake and use the sample solution as the test solution to measure Hg at the same time according to the operation process For the fluorescence signals of As and As, obtain the concentration of the corresponding element according to the respective standard curve and calculate the content of each element in the sample. The results are shown in Table 2.

Table 2. Simultaneous determination of soil Hg / As

The data shows that the method and device solve the difficulty of measuring Hg and As in the soil at the same time. At the same time, it can be seen that the Hg content in the 6 samples (standard samples) differs greatly. The samples are measured and calculated sequentially from top to bottom according to Table 2. The results are consistent with the recommended content values, indicating that the device of the present invention is used to detect and eliminate To determine the severe memory effect of Hg.

In this example, the two elements coexist in the test solution. The delivery system only needs to complete the test solution delivery once, and the dual-channel system detection is also completed at one time. In this measurement operation, water is used as the carrier current without hydrochloric acid. The NaBH ₄ solution requires only 100ml -250ml is used to participate in the reaction, and the time and cost of the entire test process are greatly reduced.

Detection Example 3, Analysis of Pb

Test samples: chemical reagents calcium chloride and calcium hydroxide

Preparation of lead standard curve: first prepare 100ng / ml lead standard solution, then take this standard solution 0, 1, 2, 3, 4, 5ml in 50ml plastic quantitative bottle respectively, add 50% concentration to each solution 10ml of HCl solution, 5ml of 5% thiourea, diluted with water to the mark, the concentration of Pb in this standard series solution is 0, 2, 4, 6, 8, 10ng / ml. After shaking, the fluorescence signals of the blank and standard series solutions are measured according to the operation process, and a standard curve is produced, as shown in FIG. 9B, and FIG. 9A is the peak curve of Pb. In the operation, the carrier gas and auxiliary gas are both Ar gas. The flow rate of argon gas (outer tube) as a carrier gas is controlled to 1000-1200ml / min, and the flow rate of argon gas (inner tube) as an auxiliary gas is controlled to 400-600ml / min.

Preparation and determination of test solution: Weigh 0.2-0.3g of chemical reagent sample, transfer to a 50ml plastic quantitative bottle, add 10ml of 50% HCl and 5ml of 5% thiourea, shake for 5-10min, then dilute with water To the mark, shake and prepare the sample solution according to the volume of Table 3. According to the same operation as the standard curve measurement, the sample solution is used as the test solution to measure the fluorescence signal of the sample solution, and the concentration of Pb is obtained from the standard curve and converted into the content in the sample. The determination results of Pb in chemical reagents are shown in Table 3.

Table 3. Determination results of Pb in calcium chloride and calcium hydroxide (ng / g)

The original atomic fluorescence analysis requires very strict control of the acidity at 2% in the determination of Pb, otherwise the fluorescence signal cannot be measured, but the test solution after pretreatment is difficult to meet this requirement, and the 2% acidity test solution is at The amount of hydrogen produced after the reduction reaction is small and it is difficult to ignite. This example increases the carrier gas flow rate while carrying out the outer tube sampling. The hydrogen flame is easy to ignite. Atomic fluorescence analysis of Pb in the test solution of 10% acidity can form an obvious Pb peak curve (see Figure 9A). Detection sensitivity, to achieve the measurement of Pb.

The above detection examples show that the atomic fluorescence analysis using this new type of atomic fluorescence analysis device can be successfully used for the determination of As, Hg, Pb and Cd in various samples. The detection limit and reproducibility data of mercury measurement are listed in Table 4, indicating that the instrument of the present invention has good stability in detection.

Table 4 Hg detection limit and reproducibility data table

Industrial applicability

The water-carrying current atomic fluorescence analysis device and the atom fluorescence analysis method provided by the present invention can perform atomic fluorescence analysis using water as a current carrier, effectively overcome the memory effect, improve the sensitivity and accuracy of fluorescence detection, and can be used for arsenic and antimony , Germanium, bismuth, selenium, lead, tin, cadmium, mercury and other heavy metals detection and analysis, with industrial applicability.

Claims (29)

1. A water-borne atomic fluorescence analysis device includes an infusion system and an instrument body. The instrument body includes a housing and a reactor, an atomizer, an excitation light source, a detector, and a control system assembled in the housing, wherein the infusion system includes :

   A test solution bottle for holding the sample solution to be tested. The test solution bottle is connected to the reactor through a sample tube;

   A reagent bottle for containing the reducing agent, the reagent bottle is connected to the reactor through the reagent inlet tube;

   A water bottle for holding pure water. The water outlet of the water bottle is connected to the inlet of the sampling tube and the inlet of the reagent tube through two water inlet tubes, and the water inlet tube is controlled to feed water into the sample tube and the reagent inlet tube by a switch; and

   The infusion system does not contain a supporting device for infusion of carrier acid.
2. The water-carrying current atomic fluorescence analysis device according to claim 1, wherein the sample inlet tube and the reagent inlet tube are both liquid inlet capillaries, the water bottle is changed to two water cups, one water cup is used for holding cleaning water, and the other The water cup is used to contain the flowing water, and the liquid inlet heads of the two liquid inlet capillaries are reinserted in the two glasses of water.
3. The water-carrying current atomic fluorescence analysis device according to claim 2, wherein the two liquid inlet capillaries are connected to the reactor through a peristaltic pump, and the peristaltic pump is used to control the delivery speed and the amount of infusion of the test solution, reagents and carrier water in the liquid inlet capillary.
4. The water-borne current atomic fluorescence analysis device according to any one of claims 1 to 3, wherein the atomizer includes a quartz furnace having an outer tube and an inner tube, and the outer tube of the quartz furnace is connected to the gas outlet line of the reactor, The inner tube of the quartz furnace is connected to the argon gas line as auxiliary gas.
5. The water-carrying current atomic fluorescence analysis device according to any one of claims 1 to 4, wherein the atomizer includes a furnace support, a furnace core, a quartz furnace sheathed in the furnace core, and a furnace sheathed outside the furnace core For the outer cover, ceramic cover plate and electric furnace wire and other components, the furnace core and the outer cover of the furnace are made of insulating and heat-resistant non-metallic materials, and the components are clamped or directly assembled without screws.
6. The water-carrying current atomic fluorescence analysis device according to claim 5, wherein the upper end of the outer shell of the furnace body is provided with at least two clamping grooves, and the ceramic cover plates are provided with snaps on the side edges, and the snap fasteners and the snap grooves are engaged to lock the furnace The upper end of the outer cover is clamped with the ceramic cover plate.
7. The water-carrying atomic fluorescence analysis device according to claim 6, wherein the electric furnace wire is fitted between the ceramic cover and the mouth of the quartz furnace, and is provided between the ceramic cover and the top surface of the furnace core The ceramic insulation layer is not asbestos. The ceramic insulation layer supports and positions the electric furnace wire at the nozzle of the quartz furnace.
8. The water-carrying current atomic fluorescence analysis device according to any one of claims 5 to 7, wherein a groove body and a step are provided on the upper part of the furnace body support, and two groove holes are provided on the side wall of the groove body; the lower part of the furnace core A protrusion is provided, and the protrusion is embedded in the groove body; the inner pipe joint and the outer pipe joint of the lower part of the quartz furnace are snap-fitted in the slot holes and extend laterally; the quartz furnace is sheathed in the cavity of the furnace core The mouth of the quartz furnace protrudes upward from the top surface of the furnace core; the furnace body cover is sleeved around the furnace core, and the bottom of the furnace body cover abuts on the step of the furnace body support.
9. The water-carrying atomic fluorescence analysis device according to any one of claims 1 to 8, wherein the housing further includes an open optical ring, the optical ring includes a housing, and a mounting hole is provided on one side of the housing , Used to install the excitation light source and the detector, respectively, and the opposite side shell on the side of the installation hole is provided with a side cut groove, the side cut groove is used to transmit the light emitted by the excitation light source.
10. The water-carrying current atomic fluorescence analysis device according to claim 9, wherein the size of the side cut groove matches the adjustment range of the excitation light source, so that the characteristic spectrum emitted by the excitation light source does not illuminate the housing of the optical ring.
11. The water-borne atomic fluorescence analysis device according to claim 9 or 10, wherein a light-absorbing paper coated with a black light-absorbing material is laid on the inside of the atomic fluorometer housing facing the side cut groove of the casing.
12. The water-carrying current atomic fluorescence analysis device according to any one of claims 1 to 11, wherein the housing further includes an integrated circuit gas circuit module, which includes a bottom plate, a switching power supply mounted on the bottom plate and a vertical frame type Electrical integration unit, the vertical frame-type electrical integration unit includes a power board, a control board and a gas control board with a fixed interval in the vertical direction, an air control unit and a gas pressure gauge are installed on the gas control board, and the control board controls the gas control unit The flow rate of the gas channel; the power board modulates the power provided by the switching power supply into different ranges of DC power supply to the control board and the gas control unit.
13. The water-borne current atomic fluorescence analysis device according to claim 12, wherein the bottom plate and the bottom of the instrument body are nested with slide rails and grooves to achieve displacement.
14. The water-borne current atomic fluorescence analysis device according to any one of claims 1 to 13, wherein a large display screen is provided on the front panel of the housing of the instrument body to display the contents of the desktop system.
15. The water-carrying current atomic fluorescence analysis device according to any one of claims 1 to 14, further comprising a lamp tube position adjustment device for adjusting the excitation light source in the horizontal direction and the vertical direction, and the adjustment knob is located in the main body casing of the instrument Side.
16. The water-carrying current atomic fluorescence analysis device according to claim 15, wherein the lamp position adjusting device comprises:

    Lamp holder, used to install the lamp;

    The support base is equipped with a lamp base on its upper surface;

    The horizontal adjustment mechanism is a gear combination structure, which is used to convert the rotation of the horizontal knob into the horizontal movement of the lamp holder with the lamp installed;

    Vertical adjustment mechanism, including a screw and a scissor structure connected to the screw through a screw nut assembly, used to convert the rotation of the screw into a change in the angle of the scissor structure to push the support seat supported on the scissor structure up and down Vertical movement

    The fixing frame is used to support the horizontal adjustment mechanism and the vertical adjustment mechanism.
17. The water-carrying current atomic fluorescence analysis device according to claim 16, wherein the two sides of the lamp holder are respectively fixed with elastic clamping pieces, the lower ends of the two clamping pieces are fixed on the side of the lamp holder, the upper end Bending to the outside, the two clamping pieces form an upper narrow opening with a narrow upper and lower accommodating space, which is used to install the lamp tube.
18. The water-borne current atomic fluorescence analysis device according to claim 16 or 17, wherein the level adjustment mechanism includes:

    The rack is fixed to the bottom of the lamp holder;

    Straight gear, equipped with integrated sleeve, and meshed with the rack;

    The lower end of the straight rack adjustment shaft is rotatably mounted on a support beam. The two ends of the support beam are fixed on the fixing frame. ;

    Two vertically arranged and meshed bevel gears, the horizontal bevel gear is fixed on the straight gear adjustment shaft, and the vertical bevel gear is fixed on the end of the bevel gear adjustment shaft;

    The horizontal knob is connected to the bevel gear adjusting shaft through a coupling.
19. The water-carrying current atomic fluorescence analysis device according to claim 18, wherein the support base comprises a horizontal plate and first side plates arranged vertically on both sides of the horizontal plate, and the spur gear is fixed in a groove opened at the bottom of the lamp base A sliding sleeve is fixed on both sides of the bottom groove of the lamp base, and the sliding sleeve can be slidably inserted into a third sliding groove opened on the horizontal plate.
20. The water-borne atomic fluorescence analysis device according to claim 19, wherein the fixing frame comprises a base, support plates fixed at both ends of the base, and second side plates provided on both sides of the base, the second side plate is provided with The mounting hole and the first chute are used to support the vertical adjustment mechanism.
21. The water-borne current atomic fluorescence analysis device according to claim 20, wherein the vertical adjustment mechanism includes:

    The scissor structure formed by the two support links, the left two corners of the scissor structure are each provided with fixing rods, and the two right corners are respectively provided with sliding rods. The mounting holes of the two side plates and the first side plate are fixed; both ends of the sliding rod are slidably sleeved in the second slide groove of the second side plate and the first slide groove of the first side plate;

    The screw and the screw nut assembly threaded on the screw and connected to the screw, the head of the screw passes through the bearing, the support plate, the screw nut assembly and is fixed in the left bearing, the tail of the screw passes a coupling It is connected to the vertical knob, and the upper end of the scissor structure formed by the two support links bears against the horizontal plate of the support base, and a sliding rod in the scissor structure passes through the screw nut and can slide through the second side plate. In the second chute.
22. An atomic fluorescence analysis method using the water-carrying current atomic fluorescence analysis device according to any one of claims 1 to 21, including using the infusion system to carry water after sampling and sampling from an outer tube of a quartz furnace using water as a carrier current and an atomization process Until the detection process is completed.
23. The atomic fluorescence analysis method according to claim 22, wherein the outer tube sampling refers to passing a mixture of mercury atoms or hydride and hydrogen gas carried by the carrier gas from the reactor into the outer tube of the quartz furnace, The auxiliary gas (Ar gas) passes into the inner tube of the quartz furnace, and controls the flow rates of the carrier gas and the auxiliary gas.
24. The atomic fluorescence analysis method according to claim 23, wherein the flow rate of the carrier gas (Ar gas) carrying the mixed gas to the outer tube is increased to 1000-1200 ml / min, and the auxiliary gas (Ar gas) to the inner tube is increased The flow rate is reduced to 400-600ml / min or no auxiliary gas is introduced (ie the flow rate is 0ml / min).
25. The atomic fluorescence analysis method according to claim 23, wherein the flow rate of the mixed gas passed into the outer tube of the quartz furnace is controlled to be uniform.
26. The atomic fluorescence analysis method according to any one of claims 22 to 25, wherein the sampling refers to simultaneously introducing a test solution of a certain acidity (hydrochloric acid concentration ranging from 4% to 10%) and a certain concentration of reagent, the Water as a carrier current means that pure water is used as a carrier current to separately carry a test solution and a reagent into the reactor.
27. The atomic fluorescence analysis method according to claim 26, wherein the sampling time is 4-5 seconds, and the water carrier current to the measurement end time is 8-10 seconds.
28. The atomic fluorescence analysis method according to claim 26, wherein two water cups are used to contain purified water, and the sampling head of the inlet capillary that transfers the test solution and reagents after sampling is inserted between the two glasses of water, sampling / delay / Replacement / Measurement time is 4-5 / 0 / 2-3 / 8-10 seconds, that is, sampling time is 4-5 seconds, delay time is zero seconds, replacement time is 2-3 seconds, and current is measured The end time is 8-10 seconds.
29. The atomic fluorescence analysis method according to any one of claims 22 to 28, characterized in that the atomization process further includes a process of controlling the intermittent ignition of the hydrogen flame, and the light source and the detector are excited during the combustion time of the hydrogen flame.

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