CN107315064A - A kind of method of cuprous oxide content in golden corrosion product for quantitative determining copper - Google Patents
A kind of method of cuprous oxide content in golden corrosion product for quantitative determining copper Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 46
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005260 corrosion Methods 0.000 title claims abstract description 45
- 230000007797 corrosion Effects 0.000 title claims abstract description 45
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 13
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 11
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 6
- 238000005259 measurement Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012086 standard solution Substances 0.000 claims description 4
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract 1
- 230000004580 weight loss Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- -1 copper ammonium ions Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
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Abstract
Description
技术领域technical field
本发明属于无机化学分析技术领域，具体地讲，本发明涉及一种定量测定铜的腐蚀产物中氧化亚铜含量的方法。The invention belongs to the technical field of inorganic chemical analysis, in particular, the invention relates to a method for quantitatively measuring the content of cuprous oxide in copper corrosion products.
背景技术Background technique
在自然环境下，铜的腐蚀产物有氧化物、硫酸盐、碳酸盐及氯化物等几种，大气环境不同，腐蚀产物也不一样。但是无论哪种大气环境，铜的腐蚀产物中一般都含有氧化亚铜，并且氧化亚铜都是铜表面形成的主要腐蚀产物之一。因此，定量分析氧化亚铜的含量，对于研究铜的腐蚀是非常重要的。目前，能够对铜的大气腐蚀产物中氧化亚铜进行定量分析的方法有恒电流阴极还原法、失重与增重比例法、红外吸收光谱法等，这些方法都有不足之处。恒电流阴极还原法在非均匀腐蚀情况下，不能准确测定氧化亚铜的含量；失重与增重比例法、红外吸收光谱法只能半定量的说明氧化亚铜的含量。而在自然环境中，铜的腐蚀一般为非均匀腐蚀，因此研究一种能够定量测定铜的腐蚀产物中氧化亚铜含量的方法具有非常现实的意义。In the natural environment, the corrosion products of copper include oxides, sulfates, carbonates and chlorides. The corrosion products are different in different atmospheric environments. But no matter what kind of atmospheric environment, the corrosion products of copper generally contain cuprous oxide, and cuprous oxide is one of the main corrosion products formed on the surface of copper. Therefore, quantitative analysis of cuprous oxide content is very important for the study of copper corrosion. At present, methods that can quantitatively analyze cuprous oxide in atmospheric corrosion products of copper include constant current cathodic reduction method, weight loss and weight gain ratio method, infrared absorption spectroscopy, etc., and these methods have shortcomings. The constant current cathodic reduction method cannot accurately determine the content of cuprous oxide under the condition of non-uniform corrosion; the weight loss and weight gain ratio method and infrared absorption spectroscopy can only semi-quantitatively explain the content of cuprous oxide. In the natural environment, the corrosion of copper is generally non-uniform corrosion, so it is of great practical significance to study a method that can quantitatively determine the content of cuprous oxide in copper corrosion products.
发明内容Contents of the invention
针对上述问题，本发明的目的是提供一种能够定量测定铜的腐蚀产物中氧化亚铜含量的方法。For the problems referred to above, the object of the present invention is to provide a method capable of quantitatively measuring the content of cuprous oxide in the corrosion products of copper.
为实现上述目的，本发明采取以下技术方案：To achieve the above object, the present invention takes the following technical solutions:
一种定量测定铜的腐蚀产物中氧化亚铜含量的方法，在无氧条件下，将待检测样品浸入氨水溶液中，使样品上的腐蚀产物(氧化亚铜及二价铜化合物)溶解在至氨水溶液中，溶解后加入硫酸酸化的硫酸铁溶液，硫酸铁将腐蚀产物氧化亚铜中亚铜离子氧化为铜离子，自身被还原为硫酸亚铁，而后在有氧环境中，用高锰酸钾标准溶液滴定硫酸亚铁，由硫酸亚铁的含量计算出氧化亚铜的含量。A method for quantitatively determining the content of cuprous oxide in copper corrosion products. Under anaerobic conditions, the sample to be tested is immersed in an ammonia solution, so that the corrosion products (cuprous oxide and divalent copper compounds) on the sample are dissolved in at least In the ammonia solution, after dissolving, add sulfuric acid acidified ferric sulfate solution, the ferric sulfate will oxidize the cuprous ions in the corrosion product cuprous oxide to copper ions, and itself will be reduced to ferrous sulfate, and then in an aerobic environment, use permanganic acid Titrate ferrous sulfate with potassium standard solution, and calculate the content of cuprous oxide from the content of ferrous sulfate.
具体：specific:
1)在无氧条件下将待检测样品浸入氨水溶液中，经振荡将铜片表面的腐蚀产物溶解至氨水溶液中，形成含铜氨络合离子的溶液；1) Under anaerobic conditions, the sample to be tested is immersed in an ammonia solution, and the corrosion product on the surface of the copper sheet is dissolved into the ammonia solution through oscillation to form a solution containing copper ammonia complex ions;
2)向上述含铜氨络合离子的溶液中加入硫酸酸化的硫酸铁溶液，在无氧条件下，利用硫酸铁中三价铁离子的氧化性，将腐蚀产物氧化亚铜中亚铜离子氧化为铜离子，而自身被还原为硫酸亚铁，而后在有氧环境中，用高锰酸钾标准溶液滴定上述形成的硫酸亚铁，根据消耗的高锰酸钾的体积及高锰酸钾的浓度，最终得到腐蚀产物中氧化亚铜的质量。2) Add ferric sulfate solution acidified by sulfuric acid to the solution containing copper ammonium complex ions, and under anaerobic conditions, use the oxidation of ferric ions in ferric sulfate to oxidize the cuprous ions in the corrosion product cuprous oxide It is copper ion, and itself is reduced to ferrous sulfate, then in an aerobic environment, titrate the above-mentioned ferrous sulfate with potassium permanganate standard solution, according to the volume of potassium permanganate consumed and the volume of potassium permanganate Concentration, finally get the mass of cuprous oxide in the corrosion product.
所述无氧条件为向体系持续通入高纯氮气(99.99％)，流量为30-200mL/min。The oxygen-free condition is to continuously feed high-purity nitrogen (99.99%) into the system, and the flow rate is 30-200mL/min.
所述氨水溶液浓度为1wt％-10wt％；所述硫酸酸化的硫酸铁溶液浓度为0.001mol/L-1mol/L。The concentration of the ammonia solution is 1wt%-10wt%; the concentration of the sulfuric acid acidified ferric sulfate solution is 0.001mol/L-1mol/L.
所依据的实验原理为：The experimental principles are based on:
Cu2O+4NH3+H2O＝2Cu(NH3)2 ++2OH- Cu 2 O+4NH 3 +H 2 O=2Cu(NH 3 ) 2 + +2OH -
3H2SO4+2OH-+2Cu(NH3)2 +＝Cu2SO4+2(NH4)2SO4+2H2O3H 2 SO 4 +2OH - +2Cu(NH 3 ) 2 + ＝Cu 2 SO 4 +2(NH 4 ) 2 SO 4 +2H 2 O
Fe2(SO4)3+Cu2SO4＝2FeSO4+2CuSO4 Fe 2 (SO 4 ) 3 +Cu 2 SO 4 ＝2FeSO 4 +2CuSO 4
2KMnO4+10FeSO4+8H2SO4＝K2SO4+5Fe2(SO4)3+2MnSO4+8H2O2KMnO 4 +10FeSO 4 +8H 2 SO 4 ＝K 2 SO 4 +5Fe 2 (SO 4 ) 3 +2MnSO 4 +8H 2 O
本发明所具有的优点：The advantages that the present invention has:
本发明能够比较准确的测定铜的腐蚀产物中氧化亚铜的含量，测量误差在±3％以内。由于本发明可以将整个铜试样表面腐蚀产物中的氧化亚铜溶解下来进行测定，因此，对于腐蚀不均匀的铜试样，依然可以准确测定其腐蚀产物中氧化亚铜的含量。依据氧化亚铜在腐蚀产物中所占的比例，可以对铜的腐蚀机理进行分析。The invention can accurately measure the cuprous oxide content in copper corrosion products, and the measurement error is within ±3%. Since the present invention can dissolve the cuprous oxide in the corrosion product on the surface of the entire copper sample for measurement, the content of the cuprous oxide in the corrosion product can still be accurately measured for a copper sample with uneven corrosion. According to the proportion of cuprous oxide in the corrosion products, the corrosion mechanism of copper can be analyzed.
本发明解决了现阶段定量测定铜的大气腐蚀产物中氧化亚铜含量的方法中，在腐蚀不均匀的情况下准确度不高的问题，具有非常重要的意义。The invention solves the problem of low accuracy in the case of uneven corrosion in the method for quantitatively measuring the content of cuprous oxide in atmospheric corrosion products of copper at the current stage, and has very important significance.
附图说明Description of drawings
图1为本发明实施例1提供的测定氧化亚铜含量的实验流程图。Fig. 1 is the experimental flow chart of measuring cuprous oxide content that the embodiment 1 of the present invention provides.
图2为本发明实施例1提供的制备的表面只有氧化亚铜的锈蚀铜片试样的XRD图Fig. 2 is the XRD pattern of the corroded copper sheet sample with only cuprous oxide on the surface prepared by the embodiment of the present invention 1
图3-为本发明实施例1提供的制备的表面只有氧化亚铜的锈蚀铜片试样的SEM图。Fig. 3 - is the SEM image of the rusted copper sheet sample with only cuprous oxide on the surface prepared in Example 1 of the present invention.
图4-为本发明实施例1提供的经过步骤1)2)后，去除表面氧化亚铜后的铜片的XRD图。Figure 4 - is the XRD pattern of the copper sheet after the surface cuprous oxide is removed after steps 1) and 2) provided in Example 1 of the present invention.
具体实施方式detailed description
下面结合附图，通过实例进一步描述本发明，但不以任何方式限制本发明。Below in conjunction with accompanying drawing, further describe the present invention by example, but do not limit the present invention in any way.
实施例1Example 1
快速制备表面只有氧化亚铜的锈蚀铜片试样：将尺寸为25mm×10mm×1mm的纯铜片用SiC抛磨纸打磨至3000目，然后采用金刚石磨抛剂抛光至1μm。将抛磨好的纯铜片放入沸腾的饱和硫酸铜溶液中静置1h，再用去离子水冲洗从硫酸铜溶液中取出锈蚀的铜片试样，并将锈蚀铜片正反面各超声波震荡20s去除表面沾着的硫酸铜试剂，然后反复用去离子水冲洗，干燥，在铜片表面制得一层均匀致密的氧化亚铜薄膜(参见图2、图3)。称量锈蚀铜片质量为3.961267gQuickly prepare a rusted copper sheet sample with only cuprous oxide on the surface: polish a pure copper sheet with a size of 25mm×10mm×1mm to 3000 mesh with SiC polishing paper, and then polish it to 1 μm with a diamond abrasive. Put the polished pure copper sheet into the boiling saturated copper sulfate solution and let it stand for 1 hour, then rinse it with deionized water, take out the corroded copper sample from the copper sulfate solution, and ultrasonically vibrate the front and back of the corroded copper sheet Remove the copper sulfate reagent attached to the surface for 20s, then repeatedly rinse with deionized water, dry, and make a uniform and dense cuprous oxide film on the surface of the copper sheet (see Figure 2, Figure 3). Weigh the mass of the rusted copper sheet to be 3.961267g
按照图1所示流程：Follow the process shown in Figure 1:
1)锈蚀铜片表面腐蚀产物的溶解：采用高纯氮气(99.99％)进行除氧1h,流量为100mL/min，然后持续通高纯氮气保持体系的无氧状态，将浓度为6.5wt％的氨水溶液加入到装有锈蚀铜片的瓶中，超声波震荡，将铜片表面的腐蚀产物溶解下来。氧化亚铜中亚铜离子与氨络合，形成一价铜氨络合离子。1) Dissolution of corrosion products on the surface of the rusted copper sheet: use high-purity nitrogen (99.99%) to remove oxygen for 1 hour, the flow rate is 100mL/min, then continue to pass high-purity nitrogen to maintain the anaerobic state of the system, and the concentration is 6.5wt%. The ammonia solution is added to the bottle with the rusted copper sheet, and the ultrasonic vibration is used to dissolve the corrosion products on the surface of the copper sheet. Cuprous ions in cuprous oxide complex with ammonia to form monovalent copper ammonium complex ions.
2)去除腐蚀产物后，铜片的清洗:在无氧条件下，将除去腐蚀产物后的铜片用绳子拉上来，然后用去离子水清洗去除腐蚀产物后的铜片(参见图4)。2) After removing the corrosion product, cleaning of the copper sheet: under anaerobic conditions, pull up the copper sheet after removing the corrosion product with a rope, and then clean the copper sheet after removing the corrosion product with deionized water (see Figure 4).
3)亚铜离子的氧化：清洗完毕后，持续通高纯氮气，使“亚铜离子的氧化”步骤在无氧条件下进行，用0.01mol/L的硫酸(1.8mol/L)酸化的硫酸铁溶液将步骤1)得到的溶液中一价铜氨络离子氧化为二价铜离子，自身被还原为硫酸亚铁。3) Oxidation of cuprous ions: After cleaning, continue to pass high-purity nitrogen gas, so that the "oxidation of cuprous ions" step is carried out under anaerobic conditions, and the sulfuric acid acidified with 0.01mol/L sulfuric acid (1.8mol/L) The iron solution oxidizes the monovalent copper ammonium ions in the solution obtained in step 1) to divalent copper ions, and itself is reduced to ferrous sulfate.
4)滴定亚铁离子：上述氧化处理后，停止通高纯氮气，用浓度为1.1325×10-3mol/L高锰酸钾溶液滴定步骤3得到的溶液中的亚铁离子，消耗的高锰酸钾的体积为4.87ml。根据消耗的高锰酸钾体积及高锰酸钾的浓度最终得到腐蚀产物中氧化亚铜的质量，2KMnO4～10Fe2+～5Cu2O， 4) Titration of ferrous ions: after the above-mentioned oxidation treatment, stop passing high-purity nitrogen gas, and titrate the ferrous ions in the solution obtained in step 3 with a concentration of 1.1325×10 -3 mol/L potassium permanganate solution, the consumed permanganese Potassium acid has a volume of 4.87ml. According to the volume of potassium permanganate consumed and the concentration of potassium permanganate Finally, the mass of cuprous oxide in the corrosion product is obtained, 2KMnO 4 ～10Fe 2+ ～5Cu 2 O,
5)称量步骤2)清洗完后的铜片质量为3.959259g，锈蚀铜片失重为0.002008g。5) The mass of the copper sheet after weighing step 2) after cleaning is 3.959259g, and the weight loss of the corroded copper sheet is 0.002008g.
而后将上述测定的氧化亚铜质量跟腐蚀失重对比，来验证本发明方法的准确度(参见表1)。Then the cuprous oxide quality of above-mentioned determination is compared with corrosion weight loss, verifies the accuracy of the inventive method (referring to table 1).
表1测定的氧化亚铜的准确度The accuracy of the cuprous oxide that table 1 measures
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| CN201710133786.8A Pending CN107315064A (en) | 2017-03-08 | 2017-03-08 | A kind of method of cuprous oxide content in golden corrosion product for quantitative determining copper |
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| CN108333295A (en) * | 2017-11-30 | 2018-07-27 | 山东东岳有机硅材料股份有限公司 | A kind of chemical analysis method of Ternary copper ternary component |
| CN112051356A (en) * | 2020-09-11 | 2020-12-08 | 山东博苑医药化学股份有限公司 | Method for analyzing content of various forms of copper in copper-containing waste |
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| CN108333295A (en) * | 2017-11-30 | 2018-07-27 | 山东东岳有机硅材料股份有限公司 | A kind of chemical analysis method of Ternary copper ternary component |
| CN112051356A (en) * | 2020-09-11 | 2020-12-08 | 山东博苑医药化学股份有限公司 | Method for analyzing content of various forms of copper in copper-containing waste |
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