CN114293055A - Fluorine-free low-hygroscopicity manganese element additive - Google Patents
Fluorine-free low-hygroscopicity manganese element additive Download PDFInfo
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- CN114293055A CN114293055A CN202111655074.5A CN202111655074A CN114293055A CN 114293055 A CN114293055 A CN 114293055A CN 202111655074 A CN202111655074 A CN 202111655074A CN 114293055 A CN114293055 A CN 114293055A
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- eutectic
- manganese
- chloride
- sodium
- potassium
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000654 additive Substances 0.000 title claims abstract description 73
- 230000000996 additive effect Effects 0.000 title claims abstract description 73
- 230000005496 eutectics Effects 0.000 claims abstract description 80
- 238000002844 melting Methods 0.000 claims abstract description 52
- 230000008018 melting Effects 0.000 claims abstract description 51
- 230000004048 modification Effects 0.000 claims abstract description 28
- 238000012986 modification Methods 0.000 claims abstract description 28
- 239000012190 activator Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 16
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 16
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011667 zinc carbonate Substances 0.000 claims abstract description 14
- 235000004416 zinc carbonate Nutrition 0.000 claims abstract description 14
- 229910000010 zinc carbonate Inorganic materials 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 44
- 239000011572 manganese Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 23
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 13
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 13
- 238000004806 packaging method and process Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 11
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 10
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 10
- 235000011151 potassium sulphates Nutrition 0.000 claims description 10
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 claims description 10
- XIUMQSREFXCDGE-UHFFFAOYSA-L S(=O)(=O)([O-])O.[Na+].[Cl-].[Na+] Chemical group S(=O)(=O)([O-])O.[Na+].[Cl-].[Na+] XIUMQSREFXCDGE-UHFFFAOYSA-L 0.000 claims description 9
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- OOIOFZFKPVAMQA-UHFFFAOYSA-L potassium manganese(2+) dichloride Chemical compound [Cl-].[Mn+2].[Cl-].[K+] OOIOFZFKPVAMQA-UHFFFAOYSA-L 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- KKXBBXAHWYSVBG-UHFFFAOYSA-L dipotassium sulfate hydrochloride Chemical group Cl.[K+].[K+].[O-]S([O-])(=O)=O KKXBBXAHWYSVBG-UHFFFAOYSA-L 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- NZXYGAMPLWXULX-UHFFFAOYSA-L dipotassium hydrogen carbonate chloride Chemical compound Cl.[K+].[K+].[O-]C([O-])=O NZXYGAMPLWXULX-UHFFFAOYSA-L 0.000 claims description 6
- SDCJMBBHNJPYGW-UHFFFAOYSA-L disodium;hydrogen carbonate;chloride Chemical compound [Na+].[Na+].Cl.[O-]C([O-])=O SDCJMBBHNJPYGW-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000019359 magnesium stearate Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 38
- 239000001103 potassium chloride Substances 0.000 description 19
- 235000011164 potassium chloride Nutrition 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 235000014380 magnesium carbonate Nutrition 0.000 description 13
- 235000002639 sodium chloride Nutrition 0.000 description 12
- 229910000838 Al alloy Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 230000008961 swelling Effects 0.000 description 10
- 239000011888 foil Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000006069 physical mixture Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- SKFYTVYMYJCRET-UHFFFAOYSA-J potassium;tetrafluoroalumanuide Chemical compound [F-].[F-].[F-].[F-].[Al+3].[K+] SKFYTVYMYJCRET-UHFFFAOYSA-J 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention relates to a fluorine-free low-hygroscopicity manganese element additive which comprises the following components in percentage by mass: manganese powder: 50-90 wt%; eutectic surface modification activating agent with melting point less than or equal to 700 ℃: 1.5-48.9 wt%; magnesium carbonate or zinc carbonate: 1-8 wt%; forming lubricant: 0.1 to 0.5 wt%. The eutectic surface modification activator of the invention is melted at high temperature to form eutectic with low melting point and uniform physical property, which can further volatilize impurities such as water, acid substances and the like in chloride, effectively reduce the moisture absorption of single chloride or simple mixture, avoid deliquescence within 3 months and improve the safety of products.
Description
Technical Field
The invention belongs to the field of aluminum alloy, relates to an aluminum alloy additive, and particularly relates to a fluorine-free low-hygroscopicity manganese element additive.
Background
CN 111139382A discloses a manganese element additive for aluminum magnesium alloy and a production method thereof, and the patent is the earlier development achievement of the applicant. The patent adopts a physical mixture of potassium chloride and magnesium chloride as a fluxing agent, and overcomes the defects of the prior art in the aspects of melting speed, actual yield, efficiency, sodium content and the like of a manganese element additive in an aluminum magnesium alloy.
But the problems of the product in the using process are as follows: easy moisture absorption and short storage time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fluorine-free low-hygroscopicity manganese element additive.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the invention provides a fluorine-free low-hygroscopicity manganese element additive which comprises the following components in percentage by mass:
manganese powder: 50-90 wt%;
eutectic surface modification activator: 1.5-48.9 wt%, wherein the eutectic surface modification activating agent is a sodium sulfate-sodium chloride eutectic, a sodium chloride-potassium chloride eutectic or a sodium carbonate-sodium chloride eutectic with the melting point of less than or equal to 700 ℃; the preparation method of the eutectic surface modification activator comprises the following steps: uniformly mixing the two components forming the eutectic according to the proportion, heating to 700-730 ℃ for melting, preserving heat for 5-10 minutes, uniformly stirring, cooling, crushing and screening into powder of 20-325 meshes;
magnesium carbonate or zinc carbonate: 1-8 wt%;
forming lubricant: 0.1 to 0.5 wt%.
The invention also provides a fluorine-free sodium-free low-hygroscopicity manganese element additive which comprises the following components in percentage by mass:
manganese powder: 50-90 wt%;
eutectic surface modification activator: 1.5-48.9 wt%, wherein the eutectic surface modification activating agent is a potassium sulfate-potassium chloride eutectic or a potassium carbonate-potassium chloride eutectic or a manganese chloride-potassium chloride eutectic with the melting point of less than or equal to 700 ℃; the preparation method of the eutectic surface modification activator comprises the following steps: uniformly mixing the two components forming the eutectic according to the proportion, heating to 700-730 ℃ for melting, preserving heat for 5-10 minutes, uniformly stirring, cooling, crushing and screening into powder of 20-325 meshes;
magnesium carbonate or zinc carbonate: 1-8 wt%;
forming lubricant: 0.1 to 0.5 wt%.
Preferably, the ratio of manganese powder: 60-85 wt%;
preferably, the eutectic surface modification activator: 11.8 to 33.7 wt%,
preferably, the ratio of magnesium carbonate or zinc carbonate: 1-6 wt%;
preferably, the forming lubricant: 0.2 to 0.4 wt%.
Further, the forming lubricant is one or a mixture of more than two of barium stearate, magnesium stearate and erucamide, the purity is more than or equal to 98%, and the granularity: -100 mesh, moisture < 1.0 wt%.
Furthermore, the manganese powder used in the invention is prepared by taking electrolytic manganese pieces with purity of more than 99.7% as raw materials, crushing and screening the electrolytic manganese pieces under a closed condition (without inert gas protection), wherein the granularity is 18-200 meshes, the oxygen content is less than or equal to 0.5%, the manganese powder of the specification has a higher melting speed than the manganese powder with granularity less than 18 meshes and a smaller burning loss than the manganese powder with granularity more than 200 meshes, the manganese powder has the same yield and melting speed as the manganese powder crushed and screened under the inert gas protection, and the manganese powder has the advantages of lower cost and high cost performance.
The preparation method of the manganese element additive comprises the steps of putting materials into a mixer in proportion for mixing for 20-40 minutes, pressing the mixed materials into a round cake shape, wherein the weight of a single block is 190-1010 g, and the density is 3.5-6.0 g/cm3And (6) packaging.
Further, the eutectic surface modification activating agent is a sodium sulfate-sodium chloride eutectic with low melting point (wherein the mass percentage of the sodium sulfate is 49-79 percent, and the melting point is less than or equal to 700 ℃), a sodium chloride-potassium chloride eutectic with low melting point (wherein the mass percentage of the sodium chloride is 13-84 percent, and the melting point is less than or equal to 700 ℃), a sodium carbonate-sodium chloride eutectic with low melting point (wherein the mass percentage of the sodium carbonate is 39-71 percent, and the melting point is less than or equal to 700 ℃), the low-melting-point eutectic of potassium sulfate and potassium chloride (wherein the mass percentage of the potassium sulfate is 40-47%, and the melting point is less than or equal to 700 ℃), the low-melting-point eutectic of potassium carbonate and potassium chloride (wherein the mass percentage of the potassium carbonate is 33-64%, and the melting point is less than or equal to 700 ℃), and the low-melting-point eutectic of manganese chloride and potassium chloride (wherein the mass percentage of the manganese chloride is 21-99%, and the melting point is less than or equal to 700 ℃).
The eutectic surface modification activating agent prepared by the melting method can further volatilize impurities such as residual moisture, acidic substances and the like in the chloride, solves the problem that the chloride is easy to absorb moisture, and has good safety.
The invention adopts magnesium carbonate and zinc carbonate as swelling agent, and compared with high-melting-point and high-decomposition-temperature carbonates such as sodium carbonate, potassium carbonate and barium carbonate, the magnesium carbonate and the zinc carbonate are decomposed at about 300-350 ℃ to generate CO2So that the additive can be quickly puffed and diffused. The low decomposition temperature point swelling agent in the manganese element additive of the invention has synergistic effect with the low melting point eutectic body, and the swelling agent decomposes and releases CO when the low melting point eutectic body is melted to promote melting2The gas promotes the manganese powder to be rapidly dispersed, diffused and melted.
Further, the forming lubricant is preferably one or a mixture of two of barium stearate, magnesium stearate and erucamide.
The quality standards of the eutectic surface modification activating agent and the swelling agent used in the invention are as follows: industrial grade, purity not less than 98%, particle size: 20-325 meshes and the water content is less than 0.1 wt%.
The forming lubricant used in the invention has the following quality standard: industrial grade, purity not less than 98%, particle size: 100 meshes below zero and water content less than 1.0 percent.
The invention has the advantages and positive effects that:
1. the surface modification activator of the sodium sulfate-sodium chloride, sodium chloride-potassium chloride, sodium carbonate-sodium chloride, potassium sulfate-potassium chloride, potassium carbonate-potassium chloride and manganese chloride-potassium chloride fluoride-free and sodium-free eutectic body is melted at high temperature to form the eutectic body with low melting point and uniform physical properties, so that impurities such as residual moisture, acidic substances and the like in the chloride can be further volatilized, the moisture absorption effect of a single chloride or a simple mixture can be effectively reduced, deliquescence cannot occur within 3 months, and the safety of the product is improved.
2. The manganese element additive adopts a fluorine-free eutectic surface modification activator taking a low-melting-point eutectic of sodium sulfate-sodium chloride or sodium chloride-potassium chloride or sodium carbonate-sodium chloride or potassium sulfate-potassium chloride or potassium carbonate-potassium chloride or manganese chloride-potassium chloride as a matrix, in addition, both a swelling agent and a forming lubricant are fluorine-free compounds, no fluoride pollution is caused after the use, the environmental protection property of the product is improved, in addition, the low-melting-point eutectic of the potassium sulfate-potassium chloride or potassium carbonate-potassium chloride or manganese chloride-potassium chloride is sodium-free, the sodium content is not increased after the use, and the applicability of the product is improved.
3. The manganese chloride-potassium chloride eutectic surface modification activator can also perform a displacement reaction with aluminum to generate AlCl by means of a formula (1)3The gas plays a role in puffing, promotes the diffusion and the melting of Mn powder, can generate Mn element, further improves the actual yield of the Mn element, and improves the effective utilization value of the material.
3MnCl2+2Al＝2AlCl3↑+3Mn (1)
4. The invention adopts magnesium carbonate and zinc carbonate as bulking agent, and sodium carbonate, potassium carbonate and carbonCompared with high-melting-point and high-decomposition-temperature carbonates such as barium carbonate, magnesium carbonate and zinc carbonate are decomposed at about 300-350 ℃ to generate CO2So that the additive can be quickly puffed and diffused. The low decomposition temperature point swelling agent and the low melting point eutectic body in the manganese element additive of the invention act synergistically, and the swelling agent decomposes to release CO2Gas, and under the action of promoting melting by melting the eutectic with low melting point, the manganese powder is rapidly dispersed, diffused and melted.
5. When the Mn content of the Mn additive is 0.1-1.2% at 720-760 ℃, the actual yield of the Mn additive can reach more than 95% in 10-30 minutes, the melting speed is high, and the actual yield is high.
Drawings
Fig. 1 is a photograph of an 85Mn additive that deliquesced.
Fig. 2 is a photograph of the 85Mn additive without deliquescence.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
In the following examples, the deliquescence detection means is mainly visual observation, after deliquescence occurs, the additive has oxidation discoloration on the surface, swelling occurs, the additive is directly pulverized into loose powder when the additive is serious, the quantitative detection is mainly moisture detection, and the moisture content after deliquescence is higher than that in a normal state. If the deliquescence starts from the production, and has a certain relation with the storage environment and the package, the deliquescence can be observed within 3-10 days under the general condition, and the maximum degree can be reached within about 1 month.
Example 1:
a fluorine-free low-hygroscopicity additive of Mn element for Al alloy contains Mn 60% (60Mn additive) and contains Mn powder 60.0%, sodium sulfate-sodium chloride eutectic 33.7%, magnesium carbonate 6.0% and barium stearate 0.3%.
The production method of the sodium sulfate-sodium chloride eutectic with low melting point comprises the following steps: mixing 400kg of total feeding materials and 50% of sodium sulfate in percentage by mass, wherein 200kg of sodium sulfate and 200kg of sodium chloride are mixed in a mixer for 10 minutes, heating the mixed materials to 700 ℃ for melting, preserving the temperature for 5 minutes, uniformly stirring, cooling, crushing and screening into 20-325-mesh powder to prepare a low-melting-point eutectic body, and the melting point is about 630 ℃;
the production method of the fluorine-free low-hygroscopicity manganese additive comprises the following steps: the sodium sulfate-sodium chloride eutectic with low melting point and other materials are mixed according to the formula proportion of the embodiment 1, each batch is 1000kg, and the materials are put into a mixer to be mixed for 20 minutes. Then, the mixed material is pressed into a round cake shape by using a hydraulic press, the weight of a single block is 500 +/-5 g, and the density: 3.8-4.2 g/cm3And packaging the manganese element additive by adopting an aluminum foil according to 2.5 kg/bag, and detecting the components, the density and the moisture of the prepared manganese element additive. No deliquescence was observed over the 3 month period.
The 60Mn additive prepared according to the example 1 is tested under the conditions that the temperature of the aluminum liquid is 730 ℃ and the Mn content is 0.8 percent, and the yield is 96.2 percent in 15 minutes.
Example 2:
a fluorine-free low-hygroscopicity additive of manganese element for aluminum alloy contains manganese 85% (85Mn additive) and its components (by mass) are manganese powder 85.0%, sodium chloride-potassium chloride low-melting-point eutectic 11.8%, zinc carbonate 3.0% and erucamide 0.2%.
The production method of the sodium chloride-potassium chloride eutectic with low melting point comprises the following steps: mixing 150kg of total feeding materials and 44% of sodium chloride in percentage by mass, wherein the sodium chloride accounts for 66kg and the potassium chloride accounts for 84kg, putting the two materials into a mixer for mixing for 10 minutes, heating the mixed materials to 700 ℃ for melting, preserving the temperature for 10 minutes, uniformly stirring, cooling, crushing and screening into 20-325-mesh powder, and preparing a low-melting-point eutectic body with a melting point of about 660 ℃;
the production method of the fluorine-free low-hygroscopicity manganese additive comprises the following steps: blending eutectic surface modification activator and other materials according to the formula proportion of the embodiment 2, wherein each batch is 1000kg, and putting the materials into a mixer for mixingMixing for 20 minutes. Then, the mixed material is pressed into a round cake shape by using a hydraulic press, the weight of a single block is 200 +/-5 g, and the density: 4.5-4.9 g/cm3And packaging by adopting aluminum foil according to a 1.0 kg/bag, and detecting the components, the density and the moisture of the prepared manganese element additive. No deliquescence was observed over the 3 month period.
The 85Mn additive prepared in example 2 was tested at 735 ℃ of aluminum liquid and 1.2% of Mn, and the yield was 96.8% in 25 minutes.
Example 3:
a fluorine-free sodium-free low-hygroscopicity additive containing manganese 75% (75 Mn) for aluminum alloy comprises, by mass, 75.0% of manganese powder, 21.7% of a low-melting-point eutectic body of potassium sulfate and potassium chloride (wherein the potassium sulfate accounts for 40% of the total mass of the eutectic body, and the potassium chloride accounts for 60% of the total mass), 3% of magnesium carbonate, 0.2% of barium stearate, and 0.1% of erucamide.
The production method of the potassium sulfate-potassium chloride eutectic with low melting point comprises the following steps: mixing 300kg of total feeding materials and 40% of potassium sulfate in percentage by mass, wherein the potassium sulfate accounts for 120kg and the potassium chloride accounts for 180kg, putting the two materials into a mixer for mixing for 10 minutes, heating the mixed materials to 720 ℃ for melting, preserving the temperature for 10 minutes, uniformly stirring, cooling, crushing and screening into 20-325-mesh powder, and preparing a low-melting-point eutectic body with a melting point of about 698 ℃;
the production method of the fluorine-free sodium-free low-hygroscopicity manganese element additive comprises the following steps: blending the eutectic surface modification activator and other materials according to the formula proportion of the invention, wherein each batch is 1000kg, and putting the materials into a mixer for mixing for 20 minutes. Then, the mixed material is pressed into a round cake shape by using a hydraulic press, the weight of a single block is 500 +/-5 g, and the density: 4.2-4.6 g/cm3, packaging with aluminum foil according to 2.5 kg/bag, and detecting the components, density and moisture of the prepared manganese element additive. No deliquescence was observed over the 3 month period.
The 75Mn additive prepared in example 3 was tested at 737 ℃ in molten aluminum with 1.1% Mn, and the yield was 96.6% in 20 minutes without increasing Na content.
Example 4:
a fluorine-free sodium-free manganese element additive for aluminum alloy comprises 85% of manganese (85Mn additive), 85.0% of manganese powder, 13.6% of manganese chloride-potassium chloride low-melting-point eutectic (wherein the manganese chloride accounts for 25% of the total mass of the eutectic, the potassium chloride accounts for 75% of the total mass), 1% of zinc carbonate, 0.1% of magnesium stearate and 0.3% of erucamide.
The production method of the low-melting-point eutectic of manganese chloride and potassium chloride comprises the following steps: mixing the two materials according to the total feeding amount of 200kg and the manganese chloride accounting for 25 percent of the total mass percent, wherein the manganese chloride accounts for 50kg and the potassium chloride accounts for 150kg, putting the two materials into a mixer for mixing for 10 minutes, heating the mixed materials to 720 ℃ for melting, preserving the temperature for 10 minutes, uniformly stirring, cooling, crushing and screening into powder of 20-325 meshes, and preparing a low-melting-point eutectic body with the melting point of about 680 ℃;
the production method of the fluorine-free sodium-free manganese additive comprises the following steps: blending the eutectic surface modification activator and other materials according to the formula proportion of the invention, wherein each batch is 1000kg, and putting the materials into a mixer for mixing for 25 minutes. Then, the mixed material was pressed into a cake shape using a hydraulic press, the weight of the single piece was 625 ± 10g, the density: 4.4-4.8 g/cm3, packaging by using a heat-shrinkable bag according to 2.5 kg/bag, and detecting the components, density and moisture of the prepared manganese element additive. No deliquescence was observed over the 3 month period.
The 85Mn additive prepared according to the embodiment 4 is tested under the conditions that the temperature of the aluminum liquid is 745 ℃ and the Mn content is 1.0 percent, the yield is 99.5 percent in 25 minutes, the actual yield is higher, and the Na content is not increased.
Comparative example 1:
a fluorine-free manganese element additive for aluminum alloy comprises 85% of manganese (85Mn additive), 85.0% of manganese powder, 11.8% of a physical mixture of sodium chloride and potassium chloride (wherein the sodium chloride accounts for 44% of the mass percentage, the potassium chloride accounts for 56% of the mass percentage), 3.0% of zinc carbonate and 0.2% of erucamide.
The production method of the fluorine-free manganese additive comprises the following steps: and (2) mixing the manganese powder, the sodium chloride, the potassium chloride, the zinc carbonate and the erucamide according to the formula proportion of the comparative example 1, wherein each batch is 1000kg, and the materials are put into a mixer for mixing for 20 minutes. Then, the mixed material is pressed into a round cake shape by using a hydraulic press, the weight of a single block is 200 +/-5 g, and the density: 4.5-4.9 g/cm3And packaging by adopting aluminum foil according to a 1.0 kg/bag, and detecting the components, the density and the moisture of the prepared manganese element additive.
The 85Mn additive prepared according to the comparative example 1 is tested under the conditions that the temperature of the aluminum liquid is 735 ℃ and the content of Mn is 1.2 percent, the yield is 85.2 percent in 30 minutes, the melting time is long compared with the embodiment 2, and the actual yield is low.
Comparative example 2:
a fluorine-free manganese element additive for aluminum alloy contains 85% of manganese (85Mn additive), 85.0% of manganese powder, 11.8% of sodium chloride-potassium chloride low-melting-point eutectic, 3.0% of barium carbonate and 0.2% of erucamide.
The production method of the sodium chloride-potassium chloride eutectic with low melting point comprises the following steps: mixing 150kg of total feeding materials and 44% of sodium chloride in percentage by mass, wherein the sodium chloride accounts for 66kg and the potassium chloride accounts for 84kg, putting the two materials into a mixer for mixing for 10 minutes, heating the mixed materials to 700 ℃ for melting, preserving the temperature for 10 minutes, uniformly stirring, cooling, crushing and screening into powder of 20-325 meshes, and preparing the eutectic surface modification activator of the eutectic with a low melting point of about 660 ℃;
the production method of the fluorine-free manganese additive comprises the following steps: blending the eutectic surface modification activator and other materials according to the formula proportion of the comparative example 2, wherein each batch is 1000kg, and putting the materials into a mixer for mixing for 20 minutes. Then, the mixed material is pressed into a round cake shape by using a hydraulic press, the weight of a single block is 200 +/-5 g, and the density: 4.5-4.9 g/cm3, packaging with aluminum foil according to a 1.0 kg/bag, and detecting the components, density and moisture of the prepared manganese element additive.
The 85Mn additive prepared according to comparative example 2 was tested at 735 ℃ of molten aluminum and 1.2% of Mn, and the yield was 94.5% in 35 minutes, since barium carbonate was used, the melting time was long compared to that of example 2.
Comparative example 3:
a fluorine-free sodium-free manganese element additive for aluminum alloy comprises 75% of manganese (75Mn additive), 75.0% of manganese powder, 21.7% of a physical mixture of potassium sulfate and potassium chloride (wherein the potassium sulfate accounts for 40% of the total mass, and the potassium chloride accounts for 60% of the total mass), 3% of magnesium carbonate, 0.2% of barium stearate and 0.1% of erucamide.
The production method of the fluorine-free sodium-free manganese additive comprises the following steps: firstly, blending manganese powder, potassium sulfate, potassium chloride, magnesium carbonate, barium stearate and erucamide which meet the requirements according to the formula proportion of a comparative example 1, wherein each batch is 1000kg, and the materials are put into a mixer for mixing for 20 minutes; pressing the mixed materials into a round cake shape by using a hydraulic press, wherein the weight of a single block is 500 +/-5 g, and the density is as follows: 4.2-4.6 g/cm3, packaging with aluminum foil according to 2.5 kg/bag, and detecting the components, density and moisture of the prepared manganese element additive. Under the same packaging and storage conditions as those of example 3, comparative example 3 exhibited moisture absorption, deliquescence, swelling of the briquette and powdering and falling off after 30 days of storage.
The 75Mn additive prepared according to the comparative example 3 was tested under the conditions that the temperature of the aluminum liquid was 737 ℃ and the Mn content was 1.1%, and the yield was 65.2% in 20 minutes and 73.5% in 30 minutes, and the Na content was not increased, and the melting rate was slow and the yield was low as compared with the example 3.
Comparative example 4:
the fluorine-containing sodium-manganese-element-containing additive for the aluminum alloy comprises 75% of manganese (75Mn additive), 75.0% of manganese powder, 21.7% of a physical mixture of sodium sulfate and sodium chloride (wherein the sodium sulfate accounts for 40% of the total mass, and the sodium chloride accounts for 60% of the total mass), 6% of sodium fluoride, 3% of magnesium carbonate, 0.2% of barium stearate and 0.1% of erucamide.
The production method comprises the following steps: firstly, mixing manganese powder, sodium sulfate, sodium chloride, sodium fluoride, magnesium carbonate, barium stearate and erucamide which meet the requirements according to the formula proportion of a comparative example 4, wherein each batch is 1000kg, and putting the materials into a mixer for mixing for 20 minutes; pressing the mixed materials into a round cake shape by using a hydraulic press, wherein the weight of a single block is 500 +/-5 g, and the density is as follows: 4.2-4.6 g/cm3, packaging with aluminum foil according to 2.5 kg/bag, and detecting the components, density and moisture of the prepared manganese element additive.
The 75Mn additive prepared according to the comparative example 4 is tested under the conditions that the temperature of aluminum liquid is 737 ℃ and the Mn content is 1.1 percent, the yield is 76.5 percent in 20 minutes and 91.2 percent in 30 minutes, the Na content after the furnace is increased by about 31ppm, the Na content is obviously increased compared with the Na content of the example 3, the Na content is beyond the general control range of the Na content in the aluminum alloy, the melting speed is slow, and the actual yield is low.
Comparative example 5:
a manganese element additive, the manganese content is 85%, its component and quality percentage content are manganese powder (granularity: 20-325 mesh, purity 99.8%) 85%, fluxing agent: 3% of potassium chloride, 3% of magnesium chloride, 2% of potassium carbonate and 2.6% of potassium tetrafluoroaluminate; forming lubricant: magnesium stearate 0.1%, oleamide 0.3%; heat generating agent: 1% of aluminum powder, 1% of magnesium powder and 2.0% of potassium nitrate.
Materials meeting the requirements are proportioned according to the formula of the invention, 1500 kg of the materials are proportioned in each batch, and the materials are put into a mixer for mixing for 20 minutes. Then, the mixed material is pressed into a round cake shape by using a hydraulic press, the weight of a single block is 200 +/-5 g, and the density: 4.6-5.0g/cm3And packaging the manganese element additive by using an aluminum foil according to a proportion of 1.0 kg/bag, and detecting the components, the density and the moisture of the prepared manganese element additive.
Under the same packaging and storage conditions as in example 2, the 85Mn additive of comparative example 5 had been hygroscopic, deliquescent, swelling and powdering of the compact and falling off when stored for 30 days, as shown in FIG. 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (7)
1. A fluorine-free low-hygroscopicity manganese element additive is characterized in that: the composition comprises the following components in percentage by mass:
manganese powder: 50-90 wt%;
eutectic surface modification activator: 1.5-48.9 wt%, wherein the eutectic surface modification activating agent is a sodium sulfate-sodium chloride eutectic, a sodium chloride-potassium chloride eutectic or a sodium carbonate-sodium chloride eutectic with the melting point of less than or equal to 700 ℃; the preparation method of the eutectic surface modification activator comprises the following steps: uniformly mixing the two components forming the eutectic according to the proportion, heating to 700-730 ℃ for melting, preserving heat for 5-10 minutes, uniformly stirring, cooling, crushing and screening into powder of 20-325 meshes;
magnesium carbonate or zinc carbonate: 1-8 wt%;
forming lubricant: 0.1 to 0.5 wt%.
2. A fluorine-free sodium-free low-hygroscopicity manganese element additive is characterized in that: the composition comprises the following components in percentage by mass:
manganese powder: 50-90 wt%;
eutectic surface modification activator: 1.5-48.9 wt%, wherein the eutectic surface modification activating agent is a potassium sulfate-potassium chloride eutectic or a potassium carbonate-potassium chloride eutectic or a manganese chloride-potassium chloride eutectic with the melting point of less than or equal to 700 ℃; the preparation method of the eutectic surface modification activator comprises the following steps: uniformly mixing the two components forming the eutectic according to the proportion, heating to 700-730 ℃ for melting, preserving heat for 5-10 minutes, uniformly stirring, cooling, crushing and screening into powder of 20-325 meshes;
magnesium carbonate or zinc carbonate: 1-8 wt%;
forming lubricant: 0.1 to 0.5 wt%.
3. The elemental manganese additive of claim 1 or 2, wherein: the forming lubricant is one or a mixture of more than two of barium stearate, magnesium stearate and erucamide, the purity is more than or equal to 98 percent, and the granularity is as follows: -100 mesh, moisture < 1.0 wt%.
4. The elemental manganese additive of claim 1 or 2, wherein: the manganese powder is prepared by taking electrolytic manganese pieces with the purity of more than 99.7 percent as raw materials, crushing and screening the electrolytic manganese pieces under the protection of non-inert gas under a closed condition, wherein the granularity is 18-200 meshes, and the oxygen content is less than or equal to 0.5 percent.
5. The elemental manganese additive of claim 1, wherein: the mass percent of sodium sulfate in the sodium sulfate-sodium chloride eutectic is 49-79%; the mass percent of sodium chloride in the sodium chloride-potassium chloride eutectic is 13-84%; the mass percent of sodium carbonate in the sodium carbonate-sodium chloride eutectic is 39-71%.
6. The elemental manganese additive of claim 2, wherein: the mass percentage of potassium sulfate in the potassium sulfate-potassium chloride eutectic is 40-47%; the mass percentage of potassium carbonate in the potassium carbonate-potassium chloride eutectic is 33-64%; the mass percentage of manganese chloride in the manganese chloride-potassium chloride eutectic is 21-99%.
7. The method for preparing manganese element additive according to claim 1 or 2, wherein: putting the materials into a mixer in proportion for mixing for 20-40 minutes, pressing the mixed materials into a round cake shape, wherein the weight of a single block is 190-1010 g, and the density is 3.5-6.0 g/cm3And (6) packaging.
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