CN111579340A - Pretreatment method and oxygen content detection method for ultra-high purity aluminum/aluminum alloy sample - Google Patents
Pretreatment method and oxygen content detection method for ultra-high purity aluminum/aluminum alloy sample Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000001514 detection method Methods 0.000 title claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 33
- 238000002203 pretreatment Methods 0.000 title claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 51
- 239000010439 graphite Substances 0.000 claims abstract description 51
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004868 gas analysis Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000001307 helium Substances 0.000 claims abstract description 7
- 229910052734 helium Inorganic materials 0.000 claims abstract description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000005554 pickling Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000013077 target material Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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Abstract
The invention provides a pretreatment method and an oxygen content detection method for an ultra-high purity aluminum/aluminum alloy sample. The pretreatment method comprises the following steps: placing the blocky ultrahigh-purity aluminum/aluminum alloy sample in hydrofluoric acid for cleaning; and then sequentially carrying out water washing, acetone washing and baking to finish pretreatment. The oxygen content detection method comprises the following steps: pretreating a blocky ultrahigh-purity aluminum/aluminum alloy sample according to the pretreatment method, then placing the pretreated sample into a graphite crucible, melting the sample at high temperature in a gas analysis detector filled with helium, respectively detecting the amount of generated carbon dioxide gas by taking the graphite crucible without the sample as a reference, and calculating the oxygen content in the sample. By selecting the block sample, the proper acid solution and the cleaning method, the invention reduces the detection error caused by insufficient oxidation or combustion of the sample and improves the accuracy of the detection result.
Description
Technical Field
The invention belongs to the technical field of ultra-high-purity metal component analysis, and particularly relates to a pretreatment method and an oxygen content detection method for an ultra-high-purity aluminum/aluminum alloy sample.
Background
Currently, Flat Panel Displays (FPDs) (including liquid crystal displays TFT-LCDs, plasma displays PDP, and touch screens TP, etc.) have become the mainstream of displays. The most critical process for producing the TFT-LCD is Physical Vapor Deposition (PVD), and the sputtering metal target material for PVD is one of important raw materials in the production of semiconductor chips and the preparation and processing process of the TFT-LCD. The sputtering deposition process of target material is one common method for producing functional film, and the sputtering process is one process of bombarding the surface of target material with high energy particles to make the atoms or molecules in the surface of the target material jet onto the surface of the substrate to form one layer of compact film.
The ultra-high purity aluminum refers to aluminum with the purity of more than 99.999 percent. Ultra-high purity aluminum and ultra-high purity aluminum alloys are the most commonly used sputtering metal targets because of their extremely high purity, excellent electrical conductivity, ease of etching, and electromigration resistance.
Magnetron sputtering coating processes are sensitive to anomalies in the gases and inclusions contained in the target, as gases and inclusions can cause plasma anomalous discharge and microscopic particle ejection, damage and reduce sputtered film quality, resulting in increased film defects. Therefore, the element content in the target material needs to be strictly controlled, so that the analysis of the element content in the ultra-high purity aluminum and the ultra-high purity aluminum alloy is particularly important.
However, ultra-high purity aluminum and ultra-high purity aluminum alloys are easily oxidized, so that the detection value of the oxygen content thereof tends to be high. Therefore, the method for improving the detection accuracy of the oxygen content in the ultra-high purity aluminum and the ultra-high purity aluminum alloy has important significance for the magnetron sputtering coating process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a pretreatment method and an oxygen content detection method for an ultra-high purity aluminum/aluminum alloy sample. The pretreatment method and the detection method can effectively reduce detection errors caused by insufficient oxidation or combustion of the ultra-high purity aluminum/aluminum alloy sample, and improve the accuracy of a detection result.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for pretreating an ultra-high purity aluminum/aluminum alloy sample, the method comprising the steps of:
(1) cleaning a block-shaped ultra-high purity aluminum/aluminum alloy sample in hydrofluoric acid at a concentration of 30-50 wt% (e.g., 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, or 50 wt%, etc.);
(2) washing the sample after acid washing with water to remove residual acid liquor;
(3) cleaning the sample after water washing with acetone to remove residual water;
(4) and baking the sample cleaned by the acetone to remove the residual acetone, thereby finishing the pretreatment.
It should be noted that the term "ultra-high purity aluminum/aluminum alloy sample" in the present invention refers to an ultra-high purity aluminum sample or an ultra-high purity aluminum alloy sample.
According to the invention, the massive sample is adopted to replace the filamentous sample, so that the specific surface area of the sample can be reduced, and the oxidation of the sample can be reduced; the inventor finds that hydrofluoric acid has higher speed of removing an oxide layer and impurities than mixed acid of nitric acid and hydrofluoric acid commonly used in the field, and is beneficial to shortening the pickling time and reducing the oxidation risk of a sample; adopt acetone to wash, it is more volatile than alcohol, can make the baking time shorten, prevents to put in the air for overlength, leads to the sample oxidation. The above factors are matched, so that the detection error caused by sample oxidation is reduced. In the invention, the concentration of hydrofluoric acid needs to be kept in a specific range, when the concentration of HF is too high, the surface of the sample after acid washing is black (instead of white of aluminum), and the detection error of oxygen content is large; too low a concentration of HF results in slow reaction, longer pickling times and increased risk of sample oxidation.
As a preferred technical scheme of the invention, the temperature of acid washing in the step (1) is 18-30 ℃; for example, the temperature may be 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃.
Preferably, the pickling time is 10-30 s; for example, it may be 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s, or 30 s.
Preferably, the acid washing in the step (1) is performed under ultrasonic conditions.
Preferably, the power of the ultrasound is 100 w-200 w; for example, the total weight may be 100w, 110w, 120w, 130w, 140w, 150w, 160w, 170w, 180w, 190w, 200w, or the like.
If the ultrasonic pickling time is too long, the sample is easy to oxidize, so that the oxygen content detection result is higher; if the ultrasonic pickling time is too short, the oxide layer on the surface of the sample is not cleaned completely, and the detection result is also higher.
In a preferred embodiment of the present invention, the number of washing in step (2) is 3 to 5 (e.g., 3, 4, or 5).
Preferably, the time of each water washing in the step (2) is 30-50 s; for example, it may be 30s, 32s, 35s, 38s, 40s, 42s, 45s, 48s, or 50 s.
In a preferred embodiment of the present invention, the number of times of the acetone washing in the step (3) is 2 to 4 (e.g., 2, 3, or 4).
Preferably, the time of each acetone cleaning in the step (3) is 10-30 s; for example, it may be 10s, 12s, 15s, 18s, 20s, 22s, 25s, 28s, or 30 s.
As the preferable technical scheme of the invention, the baking temperature in the step (4) is 30-50 ℃; for example, it may be 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃ or 50 ℃.
Preferably, the baking time in the step (4) is 60-120 s; for example, 60s, 62s, 65s, 68s, 70s, 72s, 75s, 78s, 80s, 82s, 85s, 88s, 90s, 95s, 100s, 105s, 110s, 115s, 120s, or the like may be used.
In the invention, the time for pickling, washing, acetone cleaning and baking is not suitable to be too long, otherwise, the sample is easy to be oxidized.
As a preferred technical scheme of the invention, the pretreatment method comprises the following steps:
(1) placing a blocky ultra-high purity aluminum/aluminum alloy sample in hydrofluoric acid with the temperature of 18-30 ℃ and the weight of 30-50%, and carrying out ultrasonic pickling for 10-30 s under the ultrasonic power of 100-200W;
(2) washing the sample after acid washing with water for 3-5 times, 30-50 s each time, and removing residual acid liquor;
(3) cleaning the washed sample with acetone for 2-4 times, 10-30 s each time, and removing residual water;
(4) and (3) placing the sample cleaned by the acetone under a heating lamp, baking for 60-120 s at the temperature of 30-50 ℃, removing residual acetone, and finishing pretreatment.
In a second aspect, the present invention provides a method for detecting oxygen content in ultra-high purity aluminum/aluminum alloy, wherein the method comprises the following steps:
(1) pretreating a blocky ultrahigh-purity aluminum/aluminum alloy sample according to the pretreatment method of the first aspect;
(2) putting the pretreated sample into a graphite crucible, then putting the graphite crucible into a gas analysis detector, introducing high-purity helium with the purity of more than 99.99% into the gas analysis detector, heating to melt the sample in a graphite crucible cavity to generate CO2Gas, CO generated by infrared detection cell2Detecting the amount; measuring CO generated by graphite crucible under the same heating condition2An amount;
(3) CO obtained according to step (2)2Calculating the oxygen content in the sample;
the calculation method in the step (3) comprises the following steps: CO obtained according to step (2)2Calculating the total oxygen mass in the graphite crucible and the sample, and the oxygen mass in the graphite crucible; the oxygen content in the sample is ═ (mass of total oxygen in the graphite crucible and sample-mass of oxygen in the graphite crucible)/(mass of sample).
Preferably, the sample amount of the pretreated sample is 0.4-0.5 g. In the invention, the mass of a detection sample of the ultra-high purity aluminum/aluminum alloy is preferably 0.4-0.5g, and if the mass of the sample is too large, the combustion is easy to be insufficient, so that the detection result is low; if the mass of the sample is too small, the specific surface area is large, oxidation is likely to occur, and the detection result is high.
Preferably, the heating temperature in step (2) is 800-1000 ℃, for example 800 ℃, 820 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃, 950 ℃, 980 ℃ or 1000 ℃ and the like; the time is 30s to 45s, and may be, for example, 30s, 32s, 33s, 35s, 36s, 38s, 40s, 42s, 43s, or 45 s.
Preferably, the number of the infrared detection cells is at least 2.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by selecting the block sample, the proper acid solution and the cleaning method, the detection error caused by insufficient oxidation or combustion of the ultra-high purity aluminum/aluminum alloy sample is reduced, and the accuracy of the oxygen content detection result is improved. The error of the method for detecting the oxygen content in the ultra-high purity aluminum/aluminum alloy is below 15%.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a pretreatment method of an ultra-high purity aluminum sample for oxygen content detection, which comprises the following steps:
(1) placing a blocky ultrahigh-purity aluminum/aluminum alloy sample in hydrofluoric acid with the temperature of 25 ℃ and the weight percent, and carrying out ultrasonic pickling for 15s under the ultrasonic power of 150W;
(2) washing the sample after acid washing with water for 5 times, 30s each time, and removing residual acid liquor;
(3) cleaning the sample after water washing with acetone for 3 times, each time for 20s, and removing residual water;
(4) and (3) placing the sample cleaned by the acetone under a heating lamp, baking for 60s at 50 ℃, removing residual acetone, and finishing pretreatment.
The embodiment also provides a method for detecting the oxygen content in the ultra-high purity aluminum, which comprises the following steps:
(1) taking 0.4g of the pretreated sample, and putting the sample into a graphite cruciblePlacing the crucible in a LECO ON836 model gas analysis detector, introducing high-purity helium with the purity of 99.99% into the LECO ON836 model gas analysis detector, heating the sample at 1000 deg.C for 30s to melt the sample in a graphite crucible cavity to generate CO2Gas, CO generated by two infrared detection cell pairs2Detecting the gas quantity; the CO generated by the graphite crucible is measured under the same heating condition by taking the graphite crucible without the sample as a reference2An amount;
(2) CO obtained according to step (2)2The total oxygen mass in the graphite crucible and the sample, and the oxygen mass in the graphite crucible were calculated, and the oxygen content in the sample was calculated according to the formula (total oxygen mass in the graphite crucible and the sample-oxygen mass in the graphite crucible)/(sample mass).
Example 2
The embodiment provides a pretreatment method of an ultra-high purity aluminum sample for oxygen content detection, which comprises the following steps:
(1) placing a blocky ultrahigh-purity aluminum/aluminum alloy sample in hydrofluoric acid with the temperature of 18 ℃ and the weight percent of 30 ℃, and carrying out ultrasonic pickling for 30s under the ultrasonic power of 100W;
(2) washing the sample after acid washing with water for 3 times, each time for 50s, and removing residual acid liquor;
(3) washing the washed sample with acetone for 4 times, 10s each time, and removing residual water;
(4) and (3) placing the sample cleaned by the acetone under a heating lamp, baking for 120s at the temperature of 30 ℃, and removing residual acetone to finish pretreatment.
The embodiment also provides a method for detecting the oxygen content in the ultra-high purity aluminum, which comprises the following steps:
(1) taking 0.5g of the pretreated sample, putting the sample into a graphite crucible, then putting the graphite crucible into a LECO ON836 model gas analysis detector, introducing high-purity helium with the purity of 99.99% into the LECO ON836 model gas analysis detector, heating the sample at 800 ℃ for 45s to melt the sample in a graphite crucible cavity to generate CO2Gas, CO generated by two infrared detection cell pairs2Gas quantity is carried outDetecting; the CO generated by the graphite crucible is measured under the same heating condition by taking the graphite crucible without the sample as a reference2An amount;
(2) CO obtained according to step (2)2The total oxygen mass in the graphite crucible and the sample, and the oxygen mass in the graphite crucible were calculated, and the oxygen content in the sample was calculated according to the formula (total oxygen mass in the graphite crucible and the sample-oxygen mass in the graphite crucible)/(sample mass).
Example 3
The embodiment provides a pretreatment method of an ultra-high purity aluminum sample for oxygen content detection, which comprises the following steps:
(1) placing a blocky ultrahigh-purity aluminum/aluminum alloy sample in hydrofluoric acid with the temperature of 30 ℃ and the weight percent of 50, and carrying out ultrasonic pickling for 10s under the ultrasonic power of 200W;
(2) washing the sample after acid washing with water for 4 times, and removing residual acid liquor for 40s each time;
(3) washing the washed sample with acetone for 2 times, each time for 30s, and removing residual water;
(4) and (3) placing the sample cleaned by the acetone under a heating lamp, baking for 90s at 40 ℃, removing residual acetone, and finishing pretreatment.
The embodiment also provides a method for detecting the oxygen content in the ultra-high purity aluminum, which comprises the following steps:
(1) taking 0.45g of the pretreated sample, putting the sample into a graphite crucible, then putting the graphite crucible into a LECO ON836 model gas analysis detector, introducing high-purity helium with the purity of 99.99% into the LECO ON836 model gas analysis detector, heating the sample at 900 ℃ for 40s to melt the sample in a graphite crucible cavity to generate CO2Gas, CO generated by two infrared detection cell pairs2Detecting the gas quantity; the CO generated by the graphite crucible is measured under the same heating condition by taking the graphite crucible without the sample as a reference2An amount;
(2) CO obtained according to step (2)2The total oxygen mass in the graphite crucible and the sample, and the oxygen mass in the graphite crucible are calculated, and the oxygen content in the sample is calculated according to the formula(total oxygen mass in graphite crucible and sample-oxygen mass in graphite crucible)/(sample mass), the oxygen content in the sample was calculated.
Example 4
The embodiment provides a pretreatment method of an ultra-high purity aluminum alloy sample for oxygen content detection, which comprises the following steps:
(1) placing a blocky ultrahigh-purity aluminum/aluminum alloy sample in hydrofluoric acid with the temperature of 22 ℃ and the weight percent, and carrying out ultrasonic pickling for 20s under the ultrasonic power of 180W;
(2) washing the sample after acid washing with water for 5 times, 30s each time, and removing residual acid liquor;
(3) washing the washed sample with acetone for 3 times, each time for 25s, and removing residual water;
(4) and (3) placing the sample cleaned by the acetone under a heating lamp, baking for 90s at 50 ℃, removing residual acetone, and finishing pretreatment.
The embodiment also provides a method for detecting the oxygen content in the ultra-high purity aluminum, which comprises the following steps:
(1) taking 0.45g of the pretreated sample, putting the sample into a graphite crucible, then putting the graphite crucible into a LECO ON836 model gas analysis detector, introducing high-purity helium with the purity of 99.99% into the LECO ON836 model gas analysis detector, heating the sample at 1000 ℃ for 30s to melt the sample in a graphite crucible cavity to generate CO2Gas, CO generated by two infrared detection cell pairs2Detecting the gas quantity; the CO generated by the graphite crucible is measured under the same heating condition by taking the graphite crucible without the sample as a reference2An amount;
(2) CO obtained according to step (2)2The total oxygen mass in the graphite crucible and the sample, and the oxygen mass in the graphite crucible were calculated, and the oxygen content in the sample was calculated according to the formula (total oxygen mass in the graphite crucible and the sample-oxygen mass in the graphite crucible)/(sample mass).
Comparative example 1
The difference from example 1 is that the concentration of hydrofluoric acid is 55 wt%.
Comparative example 2
The difference from example 1 is that the concentration of hydrofluoric acid is 25 wt%.
Comparative example 3
The difference from example 1 is that the mass of the test sample was 0.35 g.
Comparative example 4
The difference from example 1 is that the mass of the test sample was 0.55 g.
Comparative example 5
The difference from example 1 is that HNO is used3Mixed acid solution of HF instead of hydrofluoric acid, wherein HNO3Has a concentration of 65 wt% and a concentration of hydrofluoric acid of 40 wt%.
The results of measuring the oxygen contents of the samples of examples 1 to 4 and comparative examples 1 to 5 are shown in the following table 1:
TABLE 1
| Standard value (ppm) | Detection value (ppm) | Error of the measurement | |
| Example 1 | 1 | 1.15 | 15％ |
| Example 2 | 1 | 1.12 | 12％ |
| Example 3 | 1 | 1.06 | 6％ |
| Example 4 | 1 | 1.02 | 2％ |
| Comparative example 1 | 1 | 1.22 | 22％ |
| Comparative example 2 | 1 | 1.34 | 34％ |
| Comparative example 3 | 1 | 1.36 | 36％ |
| Comparative example 4 | 1 | 0.85 | 15％ |
| Comparative example 5 | 1 | 1.20 | 20％ |
As can be seen from the results in Table 1, the method for detecting the oxygen content in the ultra-high purity aluminum/aluminum alloy provided by the invention has the advantages that the detection result error is within 15%, and the accuracy is high.
Compared with the example 1, when the concentration of the hydrofluoric acid is too high (comparative example 1), the surface of the sample after the acid washing is black, the oxygen content detection result is higher, and the error is larger; when the concentration of the hydrofluoric acid is too low (comparative example 2), the reaction is slow, the oxide layer on the surface of the sample is not completely removed, the oxygen content detection result is higher, and the error is larger.
When the mass of the detected sample is too large (comparative example 4), the oxygen content detection value is low and the error is large because the sample is not combusted sufficiently; when the mass of the test sample was too small (comparative example 3), the oxygen content detection value was high and the error was large because the sample was more easily oxidized.
When HNO is used, as compared with example 13When the mixed acid solution of HF and HF replaces hydrofluoric acid (comparative example 5), the etching rate of the mixed acid is slow, and the oxide layer and impurities on the surface of the sample are not completely removed, so that the oxygen content detection value is higher and the error is larger.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The method for pretreating the ultrahigh-purity aluminum/aluminum alloy sample is characterized by comprising the following steps of:
(1) placing a blocky ultrahigh-purity aluminum/aluminum alloy sample in hydrofluoric acid for cleaning, wherein the concentration of the hydrofluoric acid is 30-50 wt%;
(2) washing the sample after acid washing with water to remove residual acid liquor;
(3) cleaning the sample after water washing with acetone to remove residual water;
(4) and baking the sample cleaned by the acetone to remove the residual acetone, thereby finishing the pretreatment.
2. The pretreatment method according to claim 1, wherein the temperature of the acid washing in the step (1) is 18 to 30 ℃;
preferably, the pickling time is 10-30 s;
preferably, the acid washing in the step (1) is performed under ultrasonic conditions;
preferably, the power of the ultrasonic wave is 100-200W.
3. The pretreatment method according to claim 1 or 2, wherein the number of times of the water washing in step (2) is 3 to 5;
preferably, the time of each water washing in the step (2) is 30-50 s.
4. The pretreatment method according to any one of claims 1 to 3, wherein the acetone washing in step (3) is performed 2 to 4 times;
preferably, the time of each acetone washing in the step (3) is 10s to 30 s.
5. The pretreatment method according to any one of claims 1 to 4, wherein the baking temperature in the step (4) is 30 ℃ to 50 ℃;
preferably, the baking time in the step (4) is 60s to 120 s.
6. The pretreatment method according to any one of claims 1 to 5, wherein the pretreatment method comprises the steps of:
(1) placing a blocky ultra-high purity aluminum/aluminum alloy sample in hydrofluoric acid with the temperature of 18-30 ℃ and the weight of 30-50%, and carrying out ultrasonic pickling for 10-30 s under the ultrasonic power of 100-200W;
(2) washing the sample after acid washing with water for 3-5 times, 30-50 s each time, and removing residual acid liquor;
(3) cleaning the washed sample with acetone for 2-4 times, 10-30 s each time, and removing residual water;
(4) and (3) placing the sample cleaned by the acetone under a heating lamp, baking for 60-120 s at the temperature of 30-50 ℃, removing residual acetone, and finishing pretreatment.
7. The method for detecting the oxygen content in the ultra-high purity aluminum/aluminum alloy is characterized by comprising the following steps of:
(1) pretreating a blocky ultra-high purity aluminum/aluminum alloy sample according to the pretreatment method of any one of claims 1 to 6;
(2) putting the pretreated sample into a graphite crucible, then putting the graphite crucible into a gas analysis detector of LECO ON836 type, introducing high-purity helium gas with the purity of more than 99.99% into the gas analysis detector, heating to melt the sample in a graphite crucible cavity to generate CO2Gas, CO generated by infrared detection cell2Detecting the amount; measuring CO generated by graphite crucible under the same heating condition2An amount;
(3) CO obtained according to step (2)2Calculating the oxygen content in the sample;
the oxygen content in the sample is calculated according to the following formula:
the oxygen content in the sample is ═ (mass of oxygen in the graphite crucible and sample-mass of oxygen in the graphite crucible)/(mass of sample).
8. The detection method according to claim 7, wherein the sample amount of the pretreated sample is 0.4 to 0.5 g.
9. The detection method according to claim 7 or 8, wherein the heating in the step (2) is performed at a temperature of 800 to 1000 ℃ for 30 to 45 seconds.
10. The detection method according to any one of claims 7 to 9, wherein the number of infrared detection cells is at least 2.
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