CN103792223A - Elemental analysis determination method and device - Google Patents
Elemental analysis determination method and device Download PDFInfo
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- CN103792223A CN103792223A CN201410031971.2A CN201410031971A CN103792223A CN 103792223 A CN103792223 A CN 103792223A CN 201410031971 A CN201410031971 A CN 201410031971A CN 103792223 A CN103792223 A CN 103792223A
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Abstract
The invention discloses an elemental analysis determination method and device. The elemental analysis determination method comprises the following steps: adding an inorganic compound capable of releasing hydrogen in pyrolysis into a to-be-detected sample and mixing the inorganic compound with the sample uniformly; carrying out pyrolysis on the mixture at a certain temperature, enabling an element to form a volatile matter, and determining the volatile matter by an atom spectrogram, wherein the inorganic compound for releasing hydrogen in pyrolysis is sodium bisulfide, potassium hydrogen sulfide, ammonium sulfide, ammonia hydrogen sulfide, ammonium iodide, hydrogen sulfide or hydrogen iodide, and the weight of the added inorganic compound is 0.2-100 times the weight of the sample. According to the invention, an inorganic hydrogen release reagent and a curie point pyrolyser are used, and the advantages of low analysis cost, less interference, high element volatile matter formation speed, high sampling efficiency of to-be-detected elements and the like are realized, and the method is a rapid and accurate analysis method.
Description
Technical field
The invention belongs to instrument analysis technology field, especially relate to a kind of method and apparatus of Element generation volatile matter during for element determination.Use the method, can make element formation volatile matter carry out sample and enter and then measure.
Background technology
Element determination is widely used in the industries such as material, food, environment, agricultural, chemical industry, geology and mineral products, belongs to one of two large classifications of analyzing and testing industry.Constituent content qualitative and quantitative in various samples is analyzed, and becomes already the eyes of industry-by-industry, is significant.
At present, to the detection of element in the sample of industry-by-industry, be mainly to use atomic spectrograph, specifically comprise atomic absorption spectrophotometer (AAS) (AAS), atomic fluorescence spectrophotometer (AFS), inductively coupled plasma atomic emission spectrum (ICP-AES) and inductively coupled plasma mass spectrum (ICP-MS).
Use the mensuration of above-mentioned atomic spectrum to poisonous and harmful element, the common weak point existing is: these instruments all can only be measured aqueous sample conventionally, if sample is solid sample, the overwhelming majority needs sample to clear up and make it to become aqueous solution before mensuration, so-called Specimen eliminating (or sample pre-treatments).In just making to detect, there is disadvantage in this:
(1) the Specimen eliminating time oversize, make whole detection speed slack-off, can not meet the detection demand of growing a large amount of samples.Solid sample is cleared up (sample pre-treatments) and has been occupied 60-70% of the whole sample determination time: on sample, Instrument measuring only needs a few minutes to tens minute conventionally, the needed time of Specimen eliminating before this is no less than several hours, the time that some sample pre-treatments even spend is longer, needs more expensive pre-processing device.Such as clearing up of mercury just needs airtight microwave digestion instrument.
(2) Specimen eliminating will use the high chemical reagent of price comparison conventionally, and this has increased again point
Analyse testing cost.At present solid sample is cleared up the nitric acid, hydrochloric acid, hydrogen peroxide, sulfuric acid, sodium carbonate, borax, NaOH of use etc. reagent all needs the reagent that purity is higher.
(3) solid sample is cleared up, have a certain amount of various acid by volatile emission in atmosphere, have waste liquid to be discharged in sanitary sewage, this has also increased the pollution of environment.
Chemical evapn generation (CVG) has been widely used in the sample entering method of atomic spectrum (AA, ICP-AES, ICP-MS, AFS).More conventional nebulization sampling method (sample introduction efficiency ﹤ 10%), CVG sample introduction has significantly improved sample introduction efficiency, is conventionally considered to approach 100%, thereby has improved sensitivity and the detection limit measured.Reported CVG method mainly comprises that (1) sodium borohydride (potassium) and some element (As, Sb, Bi etc.) react the element hydrogen compound (HG) (list of references 1-4) that generates gaseous state under acid condition; (2), under ultraviolet radiation, some small organic molecule (as formates etc.) and element reaction generate gaseous volatile (list of references 5-7).
But no matter all CVG sampling techniques at present, be hydrogenation generation or the reduction of formic acid ultraviolet, be the reaction under liquid-phase condition, be that testing sample all needs to clear up, this does not improve on detection time and reagent cost, has just improved mensuration sensitivity and has reduced detection limit.Therefore, develop the solid sample direct injected device that atomic spectrograph is used, not only can save detection time, reduce cost of determination, improve detection limit, eliminate environmental pollution simultaneously, be an important topic that has Important Economic meaning and have simultaneously Significance for Environment.
recently, the patent of invention that some the element reaction forming element volatile matter that produces hydrogen while utilizing organic cracking and then make this cracking hydrogen directly and in sample carries out element determination be in the news (CN103411892A) is proposed by the inventor.But there is following shortcoming in this invention: (1) is used organism to do cracking and release hydrogen reagent, make to analyze while mensuration organism and disturb greatlyr, must be connected to the purification plant of complicated element evaporation thing after cracker; (2) the cracking heating arrangement using is tube furnace pyrolyzer, due to the tube furnace pyrolyzer rate of heat addition slow (be raised to the needed time of cracking temperature temperature from room temperature after sample is heated and be greater than 2 seconds), make element evaporation thing on determining instrument, go out peak hangover seriously, the peak type detecting is not sharp-pointed, the measurement result time is lengthened, and accuracy is bad.
Summary of the invention
The deficiency existing in order to overcome above-identified patent, the inventor improves pyrolysis in tubular furnace device above, found that, if use some inorganic hydrogen reagent of releasing, as potassium hydrogen sulfide, NaHS, hydrogen iodide, ammonium iodide etc., use large volume Curie point pyrolyzer to carry out the cracking of element evaporation thing simultaneously and form, tool has an unexpected effect, such reagent and device, without avoiding some organic interference, also can make cracking heat up simultaneously quicker.The large volume Curie point cracker of the reagent of selecting according to the present invention and design carries out the cracking of element evaporation thing and generates, heating rate is fast (be raised to cracking temperature required time from room temperature and only need tens to hundreds of millisecond) more, the peak of element on detecting instrument is more sharp-pointed, and accuracy is better.The invention discloses following technology contents for realizing this object:
A kind of assay method of ultimate analysis, the mineral compound that it is characterized in that can discharging add cracking in testing sample time hydrogen makes itself and sample mix even, then make this potpourri carry out cracking at 450 ℃ of-980 ℃ of temperature, make element form volatile matter and measured by atomic spectrograph; The mineral compound that described cracking discharges hydrogen refers to: NaHS, potassium bisulfide, ammonium sulfide, sulfuretted hydrogen ammonia, ammonium iodide, sulfuretted hydrogen or hydrogen iodide; The 0.2-100 that the weight that wherein adds mineral compound is example weight doubly.Preferably 0.5-50 times.The element wherein surveyed refers to: arsenic, mercury, antimony, bismuth, selenium, germanium, tin, lead and tellurium.The crucible or the paper tinsel that when cracking, load sample can load the example weight between 2 milligrams to 200 milligrams.
When the sample of measuring is while being the inorganic samples in soil, mud and geology field, can do decomposing agents to the mineral acid further adding except nitric acid and perchloric acid in sample, its consumption is example weight 0.5 times to 50 times.
Described large volume Curie point pyrolyzer, its cracking crucible or paper tinsel are made up of at the Curie point material of 450 ℃-980 ℃ Curie-point temperature, preferably the Curie point material of 510 ℃-900 ℃.The crucible or the paper tinsel that when cracking, load sample can load the example weight between 2 milligrams to 200 milligrams.When element sample room tipping to be measured is loaded in Curie point crucible or wraps up in folding paper tinsel, crucible or paper tinsel contact the surface spraying of sample or are lined with one deck high molecular polymer or the nonmetal oxide coating without decomposition to element evaporation thing; Wherein nonmetal oxide coating refers to silicon dioxide, titania, alundum (Al2O3) or zirconia.The thickness of the crucible of Curie point pyrolyzer or paper tinsel wall is 0.05-1 millimeter.
With pyrolysis gas chromatograph Curie point pyrolyzer structural similarity used, in load coil on Curie point pyrolyzer of the present invention, be inserted with a quartz ampoule, on pipe, leave carrier gas inlet port pipe and outlet, the aperture position first-selection of two pipes is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.
The composition of Curie point magnetic material can be obtained by related documents.Such as, when the crucible or the paper tinsel that use pure iron to make make, its Curie-point temperature is 770 ℃; And when using iron nickel when being respectively the iron-nickel alloy of 30::70,40:60,49:51, its Curie-point temperature is respectively 610 ℃, 590 ℃, 510 ℃; In the time using the alloy that nickel-to-cobalt ratio is 40:60, its Curie-point temperature is 900 ℃.
In order to make sample have very fast heating rate, therefore, require crucible and metal forming wall thickness as far as possible little.The thickness that the crucible of sample or the wall of paper tinsel are housed is preferably between 0.05 millimeter to 1 millimeter.The size of crucible preferably meets following condition: in the time that 50 milligrams of testing samples are paved with in crucible bottom, now thickness of sample is preferably between 0.05 millimeter to 1 millimeter.Conventionally in this case, the size of crucible is between 0.5 centimetre to 1 centimetre at bottom internal diameter, and height is between 0.2 centimetre to 1 centimetre.The size of the crucible being more suitable for should be determined according to concrete testing sample character.
The instrument docking with the present invention refers to atomic spectrograph, and concrete is atomic fluorescence spectrophotometer, inductively coupled plasma atomic emission spectrum (ICP-AES), inductivity coupled plasma mass spectrometry (ICP-MS), electrothermal quartz tube Atomic absorption.
Curie point pyrolyzer of the present invention preferably will with one or several purification plant coupling, to remove the accessory substance that produces in cracking and the interference of fine particle, the setting of purification plant and size should make chaff interference can be gone out or not disturb the mensuration of element to be measured completely.
Direct injection analysis when Curie point cracker of the present invention is applicable to atomic absorption spectrometry element, testing sample needn't through clearing up become liquid and directly measure.Apparatus of the present invention are compared with current existing tube furnace pyrolyzer technology, and sample intensification heating rate is able to great raising, and it is faster that therefore element goes out peak on instrument, and peak type is more sharp-pointed, makes measurement result more accurate.There is novelty and creativeness.
The Curie point pyrolyzer of Element generation volatile matter while the present invention further discloses for element determination, it is characterized in that this cracker comprises load coil 1, quartz reaction bushing pipe 2, reaction chamber 3, reaction tube sealing-plug and sample carrier integrated apparatus 4, carrier gas inlet 5, carrier gas outlet 6, sample crucible or paper tinsel 7, the support 9 of holder 8, crucible or the paper tinsel carrying use of sample crucible or paper tinsel carrying use, wherein support and the sealing-plug connecting link of crucible or paper tinsel carrying use; The principle of work: the sample crucible that Curie point material is made or paper tinsel are subject to the magnetic fields of self-induction coil, produce eddy current and make crucible or the paper tinsel Curie-point temperature (heating-up time is less than 1 second) that is rapidly heated, at this temperature, the element in sample and to release hydrogen reagent reaction generting element volatile matter determined.
Sample crucible of the present invention or paper tinsel are made up of at the Curie point material of 450 ℃-980 ℃ (preferably 500 ℃-800 ℃) Curie-point temperature, and sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 1 second.The preferred needed time is less than 500 milliseconds, is more preferably less than 300 milliseconds.
Curie point material of the present invention refers to: the magnetic metal simple-substance of tool or metallic gold are closed, preferably iron, cobalt, nickel metal simple-substance or alloy.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, wherein element sample to be measured is directly or indirectly loaded in Curie-point pyrolysis crucible or wraps up in folding paper tinsel, is indirectly loaded in Curie point cracking crucible.When element sample room tipping to be measured is loaded in Curie point crucible or wraps up in folding paper tinsel, crucible or paper tinsel contact the surface spraying of sample or are lined with one deck high molecular polymer or the nonmetal oxide coating without decomposition to element evaporation thing; The thickness of described crucible or paper tinsel wall is 0.05-1 millimeter.Wherein nonmetal oxide refers to silicon dioxide, titania, alundum (Al2O3) or zirconia.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, aperture position first-selection when wherein carrier gas enters bushing pipe and is output from bushing pipe is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.This Curie point pyrolyzer is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.
Detailed description of the present invention below:
Curie point pyrolyzer of the present invention is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.Typical supply frequency for generation of the radio-frequency coil (load coil 1) in magnetic field is 600kHz, and power is 48W-200W.
Element sample to be measured can directly or indirectly be contained in and in Curie-point pyrolysis crucible or paper tinsel, carry out cracking, wherein directly dress refers to that Curie point cracking crucible or paper tinsel directly contact with sample, between tipping refer to that Curie point crucible or paper tinsel surface are coated with or are lining with one deck inert barriers, by making Curie point material there is no decomposition to the element evaporation thing producing, make element evaporation thing formation efficiency higher like this.Above mentioned crucible or paper tinsel surface are coated with or are lining with one deck inert barriers and refer to:
(1) contact with the direct of Curie point material by isolating sample to the spraying of crucible or paper tinsel inside surface containing the colloidal sol of inertia nonmetallic materials, its inert material refers to the nonmetal oxide that with silicon dioxide, titania, alundum (Al2O3), zirconia etc., element evaporation thing is not produced decomposition;
(2) by add sample in a small sample bag, then the pouch that this is equipped with to sample pack crucible into or the paper tinsel that folds in, remove to carry out Curie point heating pyrolyze, so also can avoid sample directly to contact Curie point material, make the element evaporation thing forming not by Curie point material breakdown.Small sample bag material composition is pure polymer membrane, paper etc., in order to reach extraordinary isolation effect, in high molecular polymer and paper, can evenly add with nonmetal fine powders such as silicon dioxide, titania, alundum (Al2O3), zirconias.
Typical quartz bushing pipe internal diameter size is that length is at 15-40 centimetres at 1 centimetre to 5 centimetres.The opening of bushing pipe can only arrange an end according to actual conditions opening, also can have opening in two ends.Aperture position when carrier gas enters bushing pipe and is output from bushing pipe can have several different methods, and first-selection is opened the side at bushing pipe two ends.Sample inlet sealing-plug should be selected temperature resistant encapsulation plug, first-selected silicone rubber seal plug.
In the present invention, because sample weighting amount is generally at several milligrams to tens milligrams, therefore the crucible that requirement is used and wraparound well rear metal forming have larger volume, therefore will select the Curie point material of Curie-point temperature higher than cracking temperature, the temperature difference can overcome cracking like this time.Therefore the sample crucible that the Curie point material of selecting is made or the Curie-point temperature of paper tinsel should be at 450 ℃ to 980 ℃.
Curie point magnetic material, the preferably Curie point magnetic material of 500 ℃ to 800 ℃, the composition of these Curie point materials can be obtained by related documents.Such as, when the crucible or the paper tinsel that use pure iron to make make, its Curie-point temperature is 770 ℃; And when using iron nickel when being respectively the iron-nickel alloy of 30::70,40:60,49:51, its Curie-point temperature is respectively 610 ℃, 590 ℃, 510 ℃; In the time using the alloy that nickel-to-cobalt ratio is 40:60, its Curie-point temperature is 900 ℃.
In order to make sample have very fast heating rate, therefore, require crucible and metal forming wall thickness as far as possible little.The thickness that the crucible of sample or the wall of paper tinsel are housed is preferably between 0.05 millimeter to 1 millimeter.The size of crucible preferably meets following condition: in the time that 50 milligrams of testing samples are paved with in crucible bottom, now thickness of sample is preferably between 0.05 millimeter to 1 millimeter.Conventionally in this case, the size of crucible is between 0.5 centimetre to 1 centimetre at bottom internal diameter, and height is between 0.2 centimetre to 1 centimetre.The size of the crucible being more suitable for should be determined according to concrete testing sample character.
The instrument docking with the present invention refers to atomic spectrograph, and concrete is atomic fluorescence spectrophotometer, inductively coupled plasma atomic emission spectrum (ICP-AES), inductivity coupled plasma mass spectrometry (ICP-MS), electrothermal quartz tube Atomic absorption.
Curie point pyrolyzer of the present invention preferably will with one or several purification plant coupling, to remove the organism that produces in cracking and the interference of fine particle, the setting of purification plant and size should make chaff interference can be gone out or not disturb the mensuration of element to be measured completely.
Direct injection analysis when Curie point cracker of the present invention is applicable to atomic absorption spectrometry element, testing sample needn't through clearing up become liquid and directly measure.Apparatus of the present invention are compared with current existing tube furnace pyrolyzer technology, and sample intensification heating rate is able to great raising, and it is faster that therefore element goes out peak on instrument, and peak type is more sharp-pointed, makes measurement result more accurate.There is novelty and creativeness.
First preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 150W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 2 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.10 milligrams of pedotheques are put into monkey (0.5 centimetre of an internal diameter of being made up of pure iron (770 ℃ of Curie-point temperatures), high 0.5 centimetre, 0.1 millimeter of wall and bottom thickness of scale, in order to reduce the decomposition of metal pair element evaporation thing, the silicon dioxide gel that inner surface of crucible spraying a layer thickness is 0.02 millimeter), then in pedotheque, add 0.1 milliliter of 40% NaHS, 10% 0.1 milliliter of thiocarbamide, (the 1+1 hydrochloric acid) of 0.1 milliliter mixes.In order to prevent sample sputter, can on sample, add a cover the paper tinsel (inside surface also sprays the silicon dioxide gel of 0.02 millimeter of a layer thickness) that a pure iron makes and compress sample.Then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing of element arsenic that cracking goes out, mercury, antimony, bismuth, selenium, germanium, tin is detected by atomic fluorescence spectrophotometer.
Second preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 120W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 1.5 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.20 milligrams of metallic iron powder samples are put into one, and by iron-nickel alloy, (iron nickel compares 30:70,610 ℃ of Curie-point temperatures) monkey (0.5 centimetre of the internal diameter made, high 0.6 centimetre, 0.05 millimeter of wall and bottom thickness of scale, in order to reduce the decomposition of metal pair element evaporation thing, the polyethylene film of crucible lining one deck salic 50%, sample is placed in polythene film bag), by sample with after a small amount of dissolving with hydrochloric acid, then in sediment sample, add 0.1 milliliter of 40% NaHS, 10% 0.1 milliliter of thiocarbamide) mix.Crucible top sidewall of crucible folder is left to small gap (being convenient to pyrolysis product volatilizes) to being close to both sides simultaneously with pliers, make sample better contact Curie point material.Crucible is put into quartz ampoule, open radio-frequency coil power supply and carry out induction heating.The arsenic mercury selenium element evaporation thing that cracking goes out is sent to electrothermal quartz tube Atomic absorption by carrier gas (argon gas, 300 ml/min) and detects after lime chloride adsorbent is removed steam.
The 3rd preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 80W, frequency 600kHz, 2 centimetres of coil heights.In coil, insert 1 centimetre of an internal diameter, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.10 milligrams of rubbish ashes are put into above an iron-nickel alloy paper tinsel (Alloy Foil composition is: iron nickel is than 40:60,590 ℃ of Curie-point temperatures, and the length and width of paper tinsel and thickness are respectively 3 centimetres, 1.5 centimetres and 50 microns; In order to reduce the decomposition of metal pair element evaporation thing, the aluminum hydroxide sol that paper tinsel inside surface spraying a layer thickness is 0.02 millimeter), after sneaking into the 30% NaHS aqueous solution of 0.1 milliliter in sample, make sample be wrapped (referring to pyrolysis gas chromatograph part) by folding the paper tinsel that sample is housed, then the folding paper tinsel that is surrounded by sample is placed on sample carrier, puts into quartz ampoule.Open radio-frequency coil power supply and carry out induction heating.The element evaporation thing that cracking goes out is carried after a silica wool filtering layer purifies by carrier gas (argon gas, 300 ml/min), and element evaporation thing plumbous, antimony is detected by ICP-MS.
The 4th preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 100W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 1.5 centimetres of internal diameters, the quartz ampoule that length is 12 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.5-20 milligram metal is cut to last sample to be put into one (ferro-cobalt compares 50:50 by ferro-cobalt, 980 ℃ of Curie-point temperatures) monkey (0.3 centimetre of the internal diameter made, high 0.6 centimetre, 0.6 millimeter of wall and bottom thickness of scale), in order to reduce the decomposition of metal pair element evaporation thing, in crucible, spray the silicon dioxide gel of one deck 0.01 millimeters thick and dry).Sample in crucible, with after diluted hydrochloric acid dissolution, is concentrated into closely dry, then sneaks into 0.2 milliliter of 40% hydrogen iodide solution.In order to prevent sample sputter, can on sample, add a cover the paper tinsel (face of contact sample also sprays the silicon dioxide gel of one deck 0.01 millimeters thick) that a pure iron is made.Then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing that cracking goes out is carried after a silica wool filtering layer purifies by carrier gas (argon gas, 250 ml/min), and the volatile matter of element bismuth and antimony is detected by inductively coupled plasma atomic emission spectrum ICP-AES.
The 5th preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 150W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 2 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in Figure of description 1 in detail.10 milligrams of mud samples are put into an iron plane being cut into by pure iron (770 ℃ of Curie-point temperatures) and spend inside (0.5 centimetre of internal diameter, 2 centimetres of length, 0.1 millimeter of thickness of scale, in order to reduce the decomposition of metal pair element evaporation thing, the silicon dioxide gel that iron plane flower surfaces externally and internally spraying a layer thickness is 0.02 millimeter is also dried), then in sample, immerse 0.1 milliliter of 50% ammonium sulfide solution, 10% 0.1 milliliter of thiocarbamide, mixes.Then crucible is placed on above crucible tray, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing that cracking goes out is by carrier gas (argon gas, 300 ml/min) carry after the condenser (condensing temperature-30 ℃) and a silica wool filtering layer purification of three level semiconductor refrigerating plant condensations, arsenic mercury element volatile matter is detected by atomic fluorescence spectrophotometer.
The 6th preferred embodiment of the present invention is:
Use a Curie point pyrolysis furnace with radio-frequency coil induction heating, radio-frequency coil power 150W, frequency 600kHz, 3 centimetres of coil heights.In coil, insert 2 centimetres of internal diameters, the quartz ampoule that length is 10 centimetres, quartz ampoule upper side has an argon gas entrance, has a carrier gas outlet below, and structure is shown in instructions Fig. 1 in detail.The thickness that a slice is made up of simple metal cobalt (or ferro-cobalt content be 50% alloy or nickel cobalt content be respectively 40% and 60% nickel cobalt (alloy)) is that the sheet metal of 1 millimeter is placed on above crucible tray, makes it the sample in silica crucible above indirect heating holder.0.5 centimetre of silica crucible internal diameter, high 0.5 centimetre, 1 millimeter of wall thickness.0.2 milliliter of water sample (being mixed with in advance 10% potassium bisulfide) sample is put into silica crucible the inside, then above sample, compress another iron foil (silicon dioxide gel that iron foil inside surface spraying a layer thickness is 0.02 millimeter) and change upper crucible.Crucible is put on crucible tray, opened radio-frequency coil power supply and carry out induction heating.The element evaporation thing that cracking goes out is carried through the condenser (condensing temperature-30 ℃) of three level semiconductor refrigerating plant condensations and detects as arrived ICP-MS by carrier gas (argon gas, 300 ml/min), and the volatile matter of element arsenic mercury selenium is detected by ICP-MS.
The advantage that the method and apparatus of Element generation volatile matter has compared with current existing technology (CN103411892A) during for element determination disclosed by the invention is:
(1) current existing utilization organism does cracking and releases hydrogen reagent, makes to analyze while mensuration organism and disturbs greatlyr, and element evaporation thing needs complicated purification plant.And this method is used mineral compound to release hydrogen reagent, when mensuration, disturb littlely, do not need purification plant or purification plant simple.
(2) current existing technology (CN103411892A) is used diamond heating, mainly by heat conduction, so the sample rate of heat addition is slow, conventionally while being raised to cracking, needed temperature is between 2-6 seconds, what therefore element evaporation thing formed is slow, duration is longer, and when mensuration, peak type is not sharp-pointed, and quantitative error is large.And the present invention uses induction heating, Curie point material heating rate fast (0.1 second-0.2 second), when element evaporation thing is measured, peak type is sharp-pointed, and quantitative error is little.
(3) current existing pyrolysis in tubular furnace technology, temperature control needs thermopair, and while therefore control, temperature fluctuation range is larger, is not easy accurate control, therefore measures precision bad.And the present invention to use Curie point material be by induction heating, in the time that temperature reaches Curie-point temperature, stop immediately heating, therefore cracking temperature can accurately be controlled, measuring accuracy is high.
(4) tubular furnace intensification cooling is slow, is unfavorable for that quick turn-on is measured and shutdown finishes mensuration, simultaneously relatively power consumption.And the present invention can overcome deficiency above.
Accompanying drawing explanation:
Fig. 1 is cracker schematic diagram of the present invention: wherein:
1. load coil; 2. quartz reaction bushing pipe; 3. reaction chamber; 4. reaction tube sealing-plug and sample carrier integrated apparatus; 5. carrier gas inlet; 6. carrier gas outlet; 7. sample crucible or paper tinsel; 8. the holder of sample crucible or paper tinsel carrying use; 9. the support of crucible or paper tinsel carrying use.
Embodiment:
Be below the detailed description of several most preferred embodiments, set forth the features and advantages of the present invention.Although the present invention only discloses by several forms, but be clear that for those of ordinary skills: to shape, the size of the part in the present invention with arrange relevant modification, increase and decrease and deletion, all belong to the core invention scope of setting forth in the claims in the present invention.Therefore, when attempt by this teach within the scope that other change under content recommendation or implementation method fall within these claims time, all belong to right category of the present invention.Wherein Curie point magnetic material is bought in magnetic metal material market or is used Efco-Northrup furnace synthetic voluntarily.
embodiment 1:
A kind of assay method of ultimate analysis, the mineral compound that it is characterized in that can discharging add cracking in testing sample time hydrogen makes itself and sample mix even, then make this potpourri carry out cracking at 800 ℃ of temperature, make element form volatile matter and measured by atomic spectrograph; The mineral compound that described cracking discharges hydrogen refers to: NaHS or hydrogen iodide; The weight that wherein adds mineral compound is example weight 15 times.The element wherein surveyed refers to: arsenic, mercury, antimony, bismuth, selenium, germanium, tin, lead and tellurium.
embodiment 2
An assay method for ultimate analysis, the mineral compound that can discharge hydrogen when adding cracking in testing sample makes itself and sample mix even, then makes this potpourri carry out cracking at 600 ℃ of temperature, makes element form volatile matter and is measured by atomic spectrograph; The mineral compound that described cracking discharges hydrogen refers to: NaHS; The weight that wherein adds mineral compound is example weight 35 times.The element wherein surveyed refers to: arsenic, mercury, antimony, bismuth, selenium, germanium, tin, lead and tellurium.
Embodiment 3
An assay method for ultimate analysis, the mineral compound that can discharge hydrogen when adding cracking in testing sample makes itself and sample mix even, then makes this potpourri carry out at a certain temperature cracking, makes element form volatile matter and is measured by atomic spectrograph; The mineral compound that described cracking discharges hydrogen refers to: potassium bisulfide or sulfuretted hydrogen; The weight that wherein adds mineral compound is example weight 50 times.The element wherein surveyed refers to: arsenic, mercury, antimony, bismuth, selenium, germanium, tin, lead and tellurium.The crucible or the paper tinsel that when cracking, load sample can load the example weight of 20 milligrams.
embodiment 4
The Curie point pyrolyzer device of determination of elemental analysis, comprise load coil 1, quartz reaction bushing pipe 2, reaction chamber 3, reaction tube sealing-plug and sample carrier integrated apparatus 4, carrier gas inlet 5, carrier gas outlet 6, paper tinsel 7, the holder 8 of sample paper tinsel carrying use, the support 9 of paper tinsel carrying use.
Sample crucible of the present invention or paper tinsel are made up of at the Curie point material of 980 ℃ Curie-point temperature, and sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 300 milliseconds.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, wherein element sample to be measured is directly or indirectly loaded in Curie-point pyrolysis and wraps up in folding paper tinsel, is indirectly loaded in Curie point cracking crucible.Element sample room to be measured tipping is loaded in Curie point while wrapping up in folding paper tinsel, and the surface spraying of paper tinsel contact sample is the nonmetal oxide coating without decomposition to element evaporation thing; The thickness of described paper tinsel wall is 0.08 millimeter.Element evaporation thing is referred to silicon dioxide, titanium dioxide, alundum (Al2O3) or zirconia without the nonmetal oxide coating of decomposition.
The Curie point pyrolyzer of Element generation volatile matter during for element determination of the present invention, aperture position first-selection when wherein carrier gas enters bushing pipe and is output from bushing pipe is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.This Curie point pyrolyzer is used for the cracking of hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.
embodiment 5
Arsenic in Soil content analysis
Accurately take 10 milligrams of pedotheques carry out arsenic mercury antimony bismuth mercury selenium tin content mensuration by the device described in preferred embodiment one.According to the content of seven elements of external standard method (using another standard sample of soil to do external standard typical curve).After using normal nitric acid-perchloric acid method to clear up sample simultaneously, record and contrast with the Atomic fluorescence spectrometry that liquid phase sodium borohydride hydride occurs, experiment shows that two method measurement results are close.Visible this method and classic method have well coincide.
embodiment 6:
analysis on amount of lead in sediment
Use the device described in preferred embodiment two to carry out the mensuration of lead content in vegetables.Accurately take 10 milligrams of vegetable samples in iron-nickel alloy monkey, above sample, compress an iron foil (silicon dioxide gel that paper tinsel inside surface spraying a layer thickness is 0.02 millimeter), then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating.The element evaporation thing that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (condensing temperature-20 ℃) and a silica wool filtering layer purification of three level semiconductor refrigeration, the volatile matter of the Element Lead in sample is detected (atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 450 ml/min, to provide hydrogen source normally to catch fire for atomizer) by atomic fluorescence.According to content plumbous in external standard method vegetables, use another vegetables standard specimen to do external standard typical curve simultaneously, measuring plumbous content is 160ppb.Be 170ppb and use normal nitric acid-perchloric acid method to clear up to record result plumbous in sample with electrothermal quartz tube atomic absorption spectrophotometer (AAS) after sample, visible this method has well identical with classic method.
embodiment 7:
the content analysis of arsenic and mercury in metal
Use the device described in preferred embodiment three to carry out the mensuration of cadmium and chromium content in coating.Use standard addition method to carry out quantitatively, result is respectively 52ppb and 68ppb, and this measurement result is with digestion procedure measurement result is identical in advance, and visible this method and classic method have well coincide.
embodiment 8:
the content analysis of tin in iron
Use the method described in preferred embodiment four.In the acticarbon of 20 milligrams of ADSORPTION OF GOLD, add and adsorb the sodium formate solution of 0.2 milliliter 10%, then using the Curie point pyrolyzer in preferred embodiment four to carry out golden cracking experiment.The golden volatile matter that cracking goes out and organism are by carrier gas (argon gas, 300 ml/min) carry after the condenser pipe device (2 ℃ of condensing temperatures) and a silica wool filtering layer purification of three level semiconductor refrigeration, in sample, the volatile matter of element gold is detected (atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 350 ml/min, to provide hydrogen source normally to catch fire for atomizer) by atomic fluorescence.According to the content of external standard method gold, measuring plumbous content is 10ppb.And use normal chloroazotic acid clear up after sample with the result that ICP-MS method records Gold Samples be 9.2ppb, visible this method has well identical with classic method.
embodiment 9:
the mensuration of arsenic in mud
Use the device described in preferred embodiment five to carry out the mensuration of arsenic content in water.Accurately taking 20 milligrams dares mud sample (in iron crucible, be lined with in advance a polyethylene film containing silicon dioxide 50% in iron crucible, water sample is placed in polythene film bag), then to adding 0.1 milliliter, 50% sulphur hydracid sodium, 10% 0.1 milliliter of thiocarbamide, 0.05 milliliter of hydrochloric acid in sample.Above sample, compress an iron foil (silicon dioxide gel that paper tinsel inside surface spraying a layer thickness is 0.02 millimeter), then crucible is put into quartz ampoule, opens radio-frequency coil power supply and carries out induction heating, and now iron crucible Curie-point temperature is 770 ℃.The element evaporation thing that cracking goes out is by carrier gas (argon gas, 300 ml/min) be loaded in atomic fluorescence atomizer and detect, for guaranteeing atomization, atomic fluorescence atomizer is connected with the hydrogen generator of hydrogen generation growing amount 450 ml/min, to provide hydrogen source normally to catch fire for atomizer).According to the content of arsenic in external standard method water, the content of measuring arsenic is 75ppb.And the Atomic fluorescence spectrometry that uses normal sodium borohydride hydride sampling system to record the result of arsenic in sample be 78ppb, visible this method has well identical with classic method.
embodiment 10:
the mensuration of underground water arsenic mercury selenium
Use the device described in preferred embodiment six to carry out the mensuration of content in water sample.Use standard pedotheque carries out appearance standard measure, result shows, it is identical with conventional Mixed Acids Digestion method measurement result that above-mentioned five element determination results are used the Atomic fluorescence spectrometry of normal sodium borohydride hydride sampling system to record, and visible this method and classic method have well coincide.
embodiment 11:
Contrast test
Take preferred embodiment one as example, the tube furnace pyrolyzer that uses respectively apparatus of the present invention (Curie point pyrolyzer) and patent (CN103411892A) to propose is measured the arsenic content in same soil, and experimental result is as following table:
Can find out from this contrast experiment, Curie point pyrolyzer of the present invention has better accuracy of measurement, measures precision and linear dependence than tube furnace pyrolyzer; It is more sharp-pointed that this cracker goes out peak, reaches cracking equilibrium temperature faster.There is very significantly advantage.
Claims (10)
1. the assay method of a ultimate analysis, it is characterized in that can discharging the mineral compound of hydrogen by add cracking in testing sample time and make it and sample mix even, then make this potpourri carry out cracking at 450 ℃ of-980 ℃ of temperature, make element form volatile matter and measured by atomic spectrograph; The mineral compound that described cracking discharges hydrogen refers to: NaHS, potassium bisulfide, ammonium sulfide, sulfuretted hydrogen ammonia, ammonium iodide, sulfuretted hydrogen or hydrogen iodide; The 0.2-100 that the weight that wherein adds mineral compound is example weight doubly.
2. the assay method of ultimate analysis described in claim 1, the weight that wherein adds mineral compound is example weight 0.5-50 times.
3. the assay method of ultimate analysis described in claim 1, the element wherein surveyed refers to: arsenic, mercury, antimony, bismuth, selenium, germanium, tin, lead and tellurium.
4. the Curie point pyrolyzer for determination of elemental analysis, it is characterized in that this cracker comprises load coil (1), quartz reaction bushing pipe (2), reaction chamber (3), reaction tube sealing-plug and sample carrier integrated apparatus (4), carrier gas inlet (5), carrier gas outlet (6), sample crucible or paper tinsel (7), the holder (8) of sample crucible or paper tinsel carrying use, the support (9) of crucible or paper tinsel carrying use, sample crucible or paper tinsel are subject to the magnetic fields of self-induction coil, produce eddy current and make crucible or the paper tinsel Curie-point temperature that is rapidly heated, at this temperature, element in sample and to release hydrogen reagent reaction generting element volatile matter determined, wherein support and the sealing-plug connecting link of crucible or paper tinsel carrying use.
5. Curie point pyrolyzer according to claim 4, while it is characterized in that element sample room tipping to be measured is loaded in Curie point crucible or wraps up in folding paper tinsel, crucible or paper tinsel contact the surface spraying of sample or are lined with one deck high molecular polymer or the nonmetal oxide coating without decomposition to element evaporation thing; Wherein nonmetal oxide coating refers to silicon dioxide, titania, alundum (Al2O3) or zirconia.
6. Curie point pyrolyzer according to claim 4, is characterized in that described crucible or the thickness of paper tinsel wall are 0.05-1 millimeter.
7. Curie point pyrolyzer according to claim 4, it is characterized in that sample crucible or paper tinsel (7) are made up of at the Curie point material of 450 ℃-980 ℃ Curie-point temperature, sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 1 second.
8. Curie point pyrolyzer according to claim 4, it is characterized in that sample crucible or paper tinsel (7) are made up of the Curie point material of 500 ℃-800 ℃ of Curie-point temperatures, sample is subject to after Curie point material heating to be raised to the needed time of Curie-point temperature from room temperature and is less than 500 milliseconds.
9. Curie point pyrolyzer according to claim 4, is characterized in that aperture position first-selection when carrier gas enters bushing pipe and is output from bushing pipe is opened in the side at bushing pipe two ends, and sample inlet sealing-plug is silicone rubber seal plug.
10. Curie point pyrolyzer according to claim 4, is characterized in that the cracking of this Curie point pyrolyzer for hydrogenous material, the element reaction to be measured in the hydrogen producing by cracking and sample, and generting element volatile matter is measured by atomic spectrograph.
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| CN104374614A (en) * | 2014-08-05 | 2015-02-25 | 天津师范大学 | Cracking-chemical steam generation sample-introduction apparatus for element determination and analysis method |
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| CN106226252A (en) * | 2016-07-15 | 2016-12-14 | 天津师范大学 | The forming method of a kind of element evaporation thing and device |
| CN108196005A (en) * | 2017-12-07 | 2018-06-22 | 中国科学院东北地理与农业生态研究所 | Carbon in a kind of organic liquid sample, nitrogen, hydrogen, sulfur content assay method |
| CN111351776A (en) * | 2020-04-08 | 2020-06-30 | 北矿检测技术有限公司 | Method for simultaneously and rapidly measuring arsenic and antimony in sodium stannate by steam generation-atomic fluorescence spectrometry |
| CN111504983A (en) * | 2020-05-07 | 2020-08-07 | 北京莱伯泰科仪器股份有限公司 | Device and method for combining thermal cracking with ICP/MS or ICP/OES |
| CN115326962A (en) * | 2022-08-15 | 2022-11-11 | 中国科学院西北生态环境资源研究院 | Device and method for measuring hydrogen isotope of hydrogen sulfide in natural gas |
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| CN116337682A (en) * | 2023-05-23 | 2023-06-27 | 江苏沙钢集团有限公司 | Method for detecting molten steel yield of ball-milled particle steel hot-pressed block by adopting quartz crucible melting |
| CN116337682B (en) * | 2023-05-23 | 2023-08-18 | 江苏沙钢集团有限公司 | Method for detecting molten steel yield of ball-milled particle steel hot-pressed block by adopting quartz crucible melting |
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Application publication date: 20140514 |