CN115367994A - Iron removal method for quartz sand for photovoltaic glass - Google Patents
Iron removal method for quartz sand for photovoltaic glass Download PDFInfo
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- CN115367994A CN115367994A CN202210996620.XA CN202210996620A CN115367994A CN 115367994 A CN115367994 A CN 115367994A CN 202210996620 A CN202210996620 A CN 202210996620A CN 115367994 A CN115367994 A CN 115367994A
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- quartz sand
- acid
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- strong acid
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000006004 Quartz sand Substances 0.000 title claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000011521 glass Substances 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 102
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005554 pickling Methods 0.000 claims description 24
- 238000000605 extraction Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000000536 complexating effect Effects 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940077239 chlorous acid Drugs 0.000 claims description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 4
- 229940005991 chloric acid Drugs 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 21
- 239000002699 waste material Substances 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 9
- 235000006408 oxalic acid Nutrition 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- -1 iron ions Chemical class 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000000622 liquid--liquid extraction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for removing iron from quartz sand for photovoltaic glass, and relates to the technical field of quartz sand purification. According to the method, the strong acid is used for replacing the traditional oxalic acid to carry out acid washing treatment on the quartz sand, so that the iron removal effect is better; the process of removing iron can be realized without heating in the process of removing iron, so that the production energy consumption is obviously reduced; the waste acid is not needed to be neutralized by acid and alkali, a large amount of byproducts are not generated, the oxidation of ferrous ions can be realized during acid washing, and the iron ions and other metal ions in the waste acid are subjected to impurity removal by adopting a copper-iron reagent, so that the recycling of the waste acid can be realized; meanwhile, the complex is subjected to liquid-liquid extraction by adopting isobutanol, the process is simple, the operation is easy, the liquid-liquid extract is easy to separate and collect, and the process is pollution-free.
Description
Technical Field
The invention relates to the technical field of quartz sand purification, in particular to a method for removing iron from quartz sand for photovoltaic glass.
Background
Photovoltaic glass, also known as ultra-white high-transmittance low-iron glass, is an essential material for packaging solar cells. Iron is an impurity in photovoltaic glass and directly affects the optical properties of the glass. The existence of the impurity iron causes the glass to be colored, the absorption of sunlight is increased, and the light transmittance of the glass is reduced; wherein the ferrous iron is strongInfrared rays are absorbed, and trivalent iron can strongly absorb ultraviolet rays. The low content of impurity iron brings high solar light transmittance, and indirectly improves the photoelectric conversion efficiency of the cell. Therefore, photovoltaic glass has strict requirements on the chemical composition of the siliceous raw material, siO 2 ≥99.5％，Al 2 O 3 ≤0.2％，Fe 2 O 3 ≤0.010％。
The quality control of the quartz sand for the photovoltaic glass mainly comprises granularity control of the quartz sand, refractory heavy mineral control of the quartz sand and a control method of iron content of the quartz sand, wherein the control of the iron content is a main difficulty, iron-containing substances exist in the quartz sand in various forms, and all ore dressing and purification methods of the quartz sand can remove iron to a certain extent, wherein the step desliming mainly removes argillaceous iron, the magnetic separation removes iron-containing minerals in ores, the gravity separation removes iron existing in the form of heavy minerals, and the flotation removes light silicates containing iron. The iron removal of the quartz sand for the photovoltaic glass is necessary, and the purification process flow with the lowest cost and the simplest process is selected by combining the chemical composition condition of the quartz sand in the actual production. For example, chinese patent publication No. CN111573680a discloses a method for removing iron from quartz sand, comprising the following steps: taking 1t of quartz sand to be treated and a reaction kettle, injecting 200kg of oxalic acid solution into the reaction kettle from the bottom of the reaction kettle by using a pump, wherein the mass fraction of the oxalic acid solution is 20%, heating to 60-80 ℃, keeping the temperature, and carrying out acid leaching for 4-8h, wherein the acid leaching process is accompanied with stirring; adding a disodium ethylene diamine tetraacetate solution with the concentration of 0.02mol/L into a reaction kettle after acid leaching, keeping the temperature for reaction for 1-2 hours, and then performing suction filtration to keep a solid phase, wherein the volume ratio of the disodium ethylene diamine tetraacetate solution to the oxalic acid solution is 1-25; and (3) adding water into the obtained solid phase for washing, wherein the amount of the added water is 200kg, stirring for 3-5min, carrying out suction filtration to retain the solid phase, and repeatedly washing for 3-4 times to obtain the target product. However, the method needs to heat to 60-80 ℃ after adding oxalic acid, the oxalic acid is expensive and has no iron removal effect as strong acid, and the method adds disodium ethylene diamine tetraacetate as a complexing agent, so that the generation cost is increased, and the generated waste acid liquid is not recycled and is not environment-friendly.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the method for removing the iron from the quartz sand for the photovoltaic glass, which has the advantages of good iron removal effect, low production cost and environmental friendliness.
The purpose of the invention is realized by the following technical scheme: a method for removing iron from quartz sand for photovoltaic glass comprises the step of carrying out acid washing on the quartz sand by using strong acid, wherein the strong acid is one or a mixture of hypochlorous acid, chloric acid, chlorous acid and perchloric acid, the concentration of the strong acid is 5-30%, and the temperature of the acid washing is less than or equal to 30 ℃.
Furthermore, the material ratio of the quartz sand to the strong acid is 100g, 500ml to 1000ml, and the acid washing time is 30 to 50min.
Further, the particle size of the quartz sand is 40-200 meshes.
Further, the method also comprises the step of recovering the pickling solution, and specifically comprises the following steps:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank;
s2, complexing: adding a copper-iron reagent into the recovered strong acid solution, adjusting the pH value of the solution to 4-7, and carrying out a complex reaction;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing, and separating an upper layer solution and a lower layer solution, wherein the lower layer solution is the recovered acid solution.
Further, the mass volume ratio of the iron-copper reagent to the recovered strong acid solution is 10 mg-50mg.
Furthermore, the time of the complex reaction is 0.5 to 2 hours.
Further, the standing time is 30-50 min.
According to the invention, strong acid with oxidability is adopted to carry out acid washing on quartz sand, and simultaneously, ferrous ions are oxidized into ferric ions, and as the strong acid has strong acidity, the strong acid also has a good iron removal effect at a low temperature, so that a room-temperature acid washing or low-temperature treatment process is adopted, the temperature is controlled below 30 ℃, and the energy consumption can be reduced. Adding a copper-iron reagent into the waste pickling liquid, carrying out ion complexation reaction on the copper-iron reagent and iron and the like in the waste pickling liquid to form a complex product of metal ions, wherein the complex is insoluble in waste acid, adding isobutanol to extract the complex, the complex is dissolved in the isobutanol, and the isobutanol is insoluble in acid liquid, so that the complex and the isobutanol can be well separated, the purpose of ion purification of the acid liquid is further achieved, and the recycling of the waste acid liquid is realized.
The invention has the following advantages:
(1) According to the method, the strong acid is used for replacing the traditional oxalic acid to carry out acid washing treatment on the quartz sand, so that the iron removal effect is better;
(2) The iron removal process is carried out at room temperature, and can be realized without heating, so that the production energy consumption is obviously reduced;
(3) The waste acid is not needed to be neutralized by acid and alkali, a large amount of byproducts are not generated, the oxidation of ferrous ions can be realized during acid washing, and the iron ions and other metal ions in the waste acid are subjected to impurity removal by adopting a copper-iron reagent, so that the recycling of the waste acid can be realized; meanwhile, the complex is subjected to liquid-liquid extraction by adopting isobutanol, the process is simple, the operation is easy, the liquid-liquid extract is easy to separate and collect, and the process is pollution-free.
Detailed Description
The invention is further described below with reference to examples, without limiting the scope of the invention to the following:
example 1: a method for removing iron from quartz sand for photovoltaic glass comprises the steps of pickling quartz sand with the particle size of 40-200 meshes by using strong acid at room temperature, wherein the strong acid is hypochlorous acid, and the concentration of the strong acid is 5%; wherein the material ratio of the quartz sand to the strong acid is 100g, 500ml, the acid washing time is 30min, and the acid washing liquid is recovered after the acid washing, specifically comprising the following steps:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank;
s2, complexing: adding a copper-iron reagent into the recovered strong acid solution and adjusting the pH value of the solution to be 4, wherein the mass-volume ratio of the iron-copper reagent to the recovered strong acid solution is 10mg;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing for 30min, and separating the upper solution from the lower solution, wherein the lower solution is the recovered acid solution.
Example 2: a method for removing iron from quartz sand for photovoltaic glass comprises the steps of pickling quartz sand with the particle size of 40-200 meshes by using strong acid at room temperature, wherein the strong acid is a mixture of chloric acid with the concentration of 30% and chlorous acid with the concentration of 5%; wherein, the material ratio of the quartz sand to the strong acid is 100g, 750ml, the pickling time is 50min, and the pickling solution is recovered after pickling, which specifically comprises the following steps:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank;
s2, complexing: adding a copper-iron reagent into the recovered strong acid solution and adjusting the pH value of the solution to be 5, wherein the mass-volume ratio of the iron-copper reagent to the recovered strong acid solution is 50mg;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing for 50min, and separating the upper solution from the lower solution, wherein the lower solution is the recovered acid solution.
Example 3: a method for removing iron from quartz sand for photovoltaic glass comprises the steps of pickling quartz sand with the particle size of 40-200 meshes by using strong acid at room temperature, wherein the strong acid is a mixture of 8% hypochlorous acid, 10% chlorous acid and 20% perchloric acid; wherein the material ratio of the quartz sand to the strong acid is 100g, 850ml, the pickling time is 38min, and the pickling solution is recovered after pickling, which specifically comprises the following steps:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank;
s2, complexing: adding a copper-iron reagent into the recovered strong acid solution and adjusting the pH value of the solution to 7, wherein the mass volume ratio of the iron-copper reagent to the recovered strong acid solution is 30mg;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing for 35min, and separating the upper solution from the lower solution, wherein the lower solution is the recovered acid solution.
Example 4: a method for removing iron from quartz sand for photovoltaic glass comprises the steps of carrying out acid pickling on quartz sand with the particle size of 40-200 meshes at room temperature by using strong acid, wherein the strong acid is a mixture of 25% hypochlorous acid, 8% chloric acid, 5% chlorous acid and 15% perchloric acid in concentration; wherein, the material ratio of the quartz sand to the strong acid is 100g:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank;
s2, complexing: adding a copper-iron reagent into the recovered strong acid solution and adjusting the pH value of the solution to be 5, wherein the mass-volume ratio of the iron-copper reagent to the recovered strong acid solution is 50mg;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing for 45min, and separating the upper solution from the lower solution, wherein the lower solution is the recovered acid solution.
The following experiments illustrate the beneficial effects of the present invention:
1. experimental methods
(1) Iron removal experiment
Adding 100g of quartz sand with the particle size of 40-200 meshes into 1000ml of strong acid for acid washing, wherein the acid washing time is 45min, and the raw material of the quartz sand contains Fe 2 O 3 The amount was 450ppm.
(2) Pickling solution recovery experiment
The pickling solution for the iron removal experiment is recovered after the pickling, and the method specifically comprises the following steps:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank, and detecting Fe 3+ And Fe 2+ The content;
s2, complexing: adding 50mg of copper-iron reagent into 1000ml of the recovered strong acid solution, adjusting the pH value of the solution to 5, and carrying out a complexing reaction for 1h;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing for 35min, separating the upper solution from the lower solution, wherein the lower solution is the recovered acid solution, and detecting Fe 3+ And (4) content.
2. The results of the experiment, as shown in table 1:
table 1: acid washing conditions and experimental results
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.
Claims (7)
1. The method for removing the iron from the quartz sand for the photovoltaic glass is characterized in that the quartz sand is subjected to acid cleaning at normal temperature by using strong acid, wherein the strong acid is one or a mixture of more of hypochlorous acid, chloric acid, chlorous acid and perchloric acid, and the concentration of the strong acid is 5-30%.
2. The method for removing iron in quartz sand for photovoltaic glass according to claim 1, wherein the material ratio of the quartz sand to the strong acid is 100g.
3. The method for removing iron from quartz sand for photovoltaic glass according to claim 1, wherein the particle size of the quartz sand is 40-200 meshes.
4. The method for removing iron from quartz sand for photovoltaic glass according to claim 1, further comprising the step of recovering the pickling solution, specifically comprising:
s1, collecting: recovering the strong acid solution obtained after the quartz sand is subjected to acid washing to a pickling tank;
s2, complexing: adding a copper-iron reagent into the recovered strong acid solution, and adjusting the pH value of the solution to 4-7 to perform a complex reaction;
s3, extraction: adding isobutanol into the complexed strong acid solution for extraction, standing, and separating an upper layer solution and a lower layer solution, wherein the lower layer solution is the recovered acid solution.
5. The method for removing iron in quartz sand for photovoltaic glass according to claim 4, wherein the mass volume ratio of the iron-copper reagent to the recovered strong acid solution is 10 mg-50mg.
6. The method for removing iron in quartz sand for photovoltaic glass according to claim 4, wherein the time of the complexation reaction is 0.5-2 h.
7. The method for removing iron in quartz sand for photovoltaic glass as claimed in claim 4, wherein the standing time is 30-50 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210996620.XA CN115367994A (en) | 2022-08-19 | 2022-08-19 | Iron removal method for quartz sand for photovoltaic glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210996620.XA CN115367994A (en) | 2022-08-19 | 2022-08-19 | Iron removal method for quartz sand for photovoltaic glass |
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| Publication Number | Publication Date |
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| CN115367994A true CN115367994A (en) | 2022-11-22 |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042501A (en) * | 1976-07-02 | 1977-08-16 | Kaiser Aluminum & Chemical Corporation | Purification of iron containing acidic solutions |
| US4219354A (en) * | 1977-11-28 | 1980-08-26 | Outokumpu Oy | Hydrometallurgical process for the treatment of oxides and ferrites which contain iron and other metals |
| CN102503130A (en) * | 2011-10-18 | 2012-06-20 | 陈俊江 | Production method for preparing composite particle glass raw material by utilizing silica powder waste and application thereof |
| CN103382087A (en) * | 2013-07-05 | 2013-11-06 | 田辉明 | Method of preparing low iron-containing quartz sand for photovoltaic glass from pyrite type quartzite and pickling purification apparatus |
| CN104556687A (en) * | 2015-02-09 | 2015-04-29 | 陈吉美 | Solar photovoltaic glass and preparation method thereof |
| CN104860318A (en) * | 2014-02-20 | 2015-08-26 | 新沂市宏润石英硅微粉有限公司 | Acid washing system for producing mixing acid oxidation high-purity quartz sand |
| CN108101357A (en) * | 2017-12-21 | 2018-06-01 | 徐维祥 | A kind of quartz sand oxalic acid remove iron after saliferous give up oxalic acid water processing and reuse method |
| CN111204768A (en) * | 2020-01-09 | 2020-05-29 | 上杭鑫昌龙实业有限公司 | Method and device for treating waste acid leached by acid in purification process of quartz tailings |
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-
2022
- 2022-08-19 CN CN202210996620.XA patent/CN115367994A/en active Pending
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|---|---|---|---|---|
| US4042501A (en) * | 1976-07-02 | 1977-08-16 | Kaiser Aluminum & Chemical Corporation | Purification of iron containing acidic solutions |
| US4219354A (en) * | 1977-11-28 | 1980-08-26 | Outokumpu Oy | Hydrometallurgical process for the treatment of oxides and ferrites which contain iron and other metals |
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| Title |
|---|
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