CN105087973A - Chromium additive for producing aluminum alloy and preparation method of chromium additive - Google Patents
Chromium additive for producing aluminum alloy and preparation method of chromium additive Download PDFInfo
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- CN105087973A CN105087973A CN201510541401.2A CN201510541401A CN105087973A CN 105087973 A CN105087973 A CN 105087973A CN 201510541401 A CN201510541401 A CN 201510541401A CN 105087973 A CN105087973 A CN 105087973A
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000011651 chromium Substances 0.000 title claims abstract description 58
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 58
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 title abstract description 51
- 230000000996 additive effect Effects 0.000 title abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000004411 aluminium Substances 0.000 claims description 70
- 239000000843 powder Substances 0.000 claims description 64
- -1 by mass percentage Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 239000013543 active substance Substances 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 24
- 230000008018 melting Effects 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 18
- 238000003825 pressing Methods 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000956 alloy Substances 0.000 description 23
- 239000007788 liquid Substances 0.000 description 19
- 229910001388 sodium aluminate Inorganic materials 0.000 description 14
- 238000005275 alloying Methods 0.000 description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000012913 prioritisation Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the field of additives for aluminum alloy and discloses a chromium additive for producing aluminum alloy and a preparation method of the chromium additive. The chromium additive for producing aluminum alloy is formed by mainly pressing chromium powder, aluminum powder and a fluxing agent and is in the shape of a cake or a football. The chromium powder and the aluminum powder are broken under the protection of inert gases. The chromium additive for producing aluminum alloy further comprises a surface active agent. Specifically, the chromium additive for producing aluminum alloy comprises, by mass, 90%-97% of the chromium powder, 2%-9.39% of the aluminum powder, 0.01%-5% of the fluxing agent and 0.5%-2% of the surface active agent. The density of the chromium agent formed by pressing all the components ranges from 2.8g/cm <3> to 5.0 g/cm <3>. The chromium content of the additive can be as high as 97%. According to the chromium agent, the melting temperature is low, an aluminum melt can melt at the temperature as low as 670 DEG C, the melting time is short, the aluminum melt can melt in ten to fifteen minutes, and the recovery rate of chromium metal can be as high as 95%.
Description
Technical field
The invention belongs to the additive agent field of aluminium alloy, be specifically related to a kind of aluminum alloy chromium additive and preparation method thereof.
Background technology
Along with aluminium processing and aluminium alloy industry development, the development of aluminium alloy is listed in the technology given priority to, and alloying is a ring important in aluminum alloy production process flow process.The dissolving of alloy Addition ofelements in molten aluminum is the significant process of alloying.The dissolving of element and its character have substantial connection, control by the destruction of Addition ofelements solid-state structure bonding force and the velocity of diffusion of atom in aluminium liquid.The alloying element that aluminium alloy is conventional has: silicon, iron, copper, magnesium, nickel, zinc, vanadium etc.Some low melting points or large alloying element such as magnesium, the copper etc. of solubleness can directly add in molten aluminium, and the high alloying element of most of fusing point is as iron, nickel, manganese etc., because the fusing point gap with aluminium is too large, directly cannot adds, need to be added by the mode of master alloy.This is because as by melting of metal such as iron, nickel, manganese, then temperature of smelting furnace must reach more than 1000 DEG C, and the fusing point of aluminium only has 660 DEG C, if at the temperature more than 1000 DEG C, then molten aluminium can be vaporized, and very easily there is chemical reaction with the oxygen, hydrogen, water etc. of surrounding at such high temperatures in the aluminium liquid of not vaporizing in smelting furnace, form the impurity being difficult to remove, alloy content and the alloy content deviation needed for reality of the aluminium alloy melt generated are excessive, thus cause alloy mechanical performance to meet the demands, cause the wasting of resources.
In order to avoid above-mentioned deficiency, temperature required when people adopt the mode of master alloy to reduce alloying element melting process.The production technique of master alloy is such: first by refined alloy, content is maximum, fusing point is lower melting of metal.Then fusing point is higher and that content is less element adds, and dissolves and makes alloy.During melting master alloy, need to add a small amount of flux protection, in order to avoid gas enters alloy, also part that can be removed impurity.Fully to stir after fusing, make ingot casting after uniform composition.Some high-quality master alloy needs in a vacuum or melting and casting under protective atmosphere.The main standard of quality quality passing judgment on aluminium alloy be in alloy whether containing impurity or foreign matter content number; desirable aluminium alloy does not have impurity; therefore impurity is more few better; therefore the quality requirements for aluminium alloy master alloy used is high; just need in a vacuum or melting burning casting under protective atmosphere; manufacturing condition requires high, and production cost is high, and efficiency reduces greatly.In addition, alloying element content contained by master alloy is lower, when weighing calculates, master alloy amount used will be larger, in order to ensure the temperature of melting master alloy, the amount of each input master alloy can not be too much, dosage too much can cause molten aluminium temperature to reduce, master alloy cannot be melted, so when producing the aluminium alloy of same model, carrying out alloying with master alloy adopts repeatedly a small amount of mode to carry out interpolation input in molten aluminium with regard to needs, will cause like this producing following problem: 1, the overlong time of fusing needed for master alloy; 2, the impurity level generated that reacts of other materials such as oxygen, hydrogen, carbon, moisture in the long-time and air of molten aluminium increases, and causes the quality of aluminium alloy to reduce; 3, fusing time length can increase energy consumption, can increase scaling loss and the air-breathing of molten aluminium.
Due to master alloy above shortcomings, people expect utilizing solubility promoter to help alloying element at low temperature i.e. about 710 DEG C molten alloy metallic elements in recent years, and people are referred to as metal additive.According to different performance requirements, in aluminium liquid, usually add, melt the alloying element of heterogeneity and content, to obtain the aluminium alloy of different model and classification.At present, alloying element has copper, silicon, magnesium, zinc, manganese, iron, chromium etc. usually.During enforcement, the temperature of aluminum alloy melt casting is generally about 710 DEG C, low melting point or the large alloying element of melting degree are directly added in aluminium liquid can be melted with the form of elemental metals powder, but for manganese, iron, the high-melting-points such as chromium or the little alloying element of melting degree, elemental metals powder is just difficult to be melted in aluminium liquid, if the temperature of aluminium liquid smelting furnace is elevated to manganese, iron, the temperature of chromium metal, aluminium liquid then in smelting furnace just can gasify, therefore solution is at the temperature that can not gasify at aluminium, fast by manganese, iron, the metals such as chromium melt, in order to reach this object, people have expected manganese, iron, chromium powder is broken, and add fusing assistant in the powder, and make solid shape, our usually said manganese agent i.e., chalybeate, chromium agent, when by manganese agent, chalybeate, chromium agent is put in aluminium liquid smelting furnace, fusing assistant formula of blasting rapidly in aluminium liquid is reacted, the heat produced can reach and make manganese within for some time, iron, the temperature that the metals such as chromium melt.But, this kind of mode needs a large amount of fusing assistants to realize, therefore in every block additive product, the content of manganese, iron, chromium is the highest can only reach about 85%, if the content of the manganese in additive product, iron, chromium is brought up to more than 90%, then the amount of corresponding fusing assistant then reduces, and joined by product after in aluminium liquid, the manganese in additive, iron, chromium can not melt completely; In addition, granularity, content proportioning etc. for powder such as manganese, iron, chromium in making processes have special requirement.For chromium, chrome content in the size distribution of iron powder of the chalybeate of 80% is: be greater than 60 order requirements below 5%, and 60-80 order is 30%-35%, 80-100 order be 15%-20%, 100-325 order is 35%-45%, is less than 325 order requirements below 10%; Above-mentioned granularity is mainly between 60-325 order, visible size-grade distribution is very narrow, usually in disintegrating process, size-grade distribution is narrower, the processing requirement pulverized is higher, so the chromium powder of above-mentioned size-grade distribution is just very high to the requirement of disintegrating process, the cost of processing is also very high, such as at shredding stage, we just need the granularity of the chromium powder of more than 85% must not be greater than 60 orders, 325 orders must not be less than simultaneously, but the particle size distribution that existing disintegrating process often can not be so strict, the chromium agent qualification rate therefore produced is usually less than 60%.Moreover, because the mean particle size of the chromium powder entirety in existing chromium line aluminium alloy additive is comparatively large, after adding aluminium liquid, because granularity is little compared with the specific surface area of large chromium powder, surface energy is also little, thus melts slower, and require that casting melting temperatur is higher, be generally about 710 DEG C.In addition, in order to avoid additive product is loose in transportation, usually additive product will be pressed into density higher pie or spherical, density is greater than 5.0g/cm usually
3but for the additive product that density is higher, after adding aluminium liquid, on the one hand, melt relatively slower, the melting time is generally 15-20min, melts the time long; On the other hand, the additive adding molten aluminium easily sinks to the bottom, once sink to the bottom, chromium powder fusing speed can be caused to slow down, and after chromium powder can be caused to dissolve, dispersion is uneven; Again on the one hand, more closely knit additive product surface in fusion processes can form fine and close protective membrane, thus causes inside cannot continue to melt, and the rate of recovery will be made so lower, the highlyest only can reach about 90%.
Summary of the invention
The technical problem to be solved in the present invention is to provide and a kind ofly melts the chromium agent for the production of aluminium alloy that the time is short, chromium recovery ratio is high.
The object of the present invention is to provide following base case: a kind of chromium agent for the production of aluminium alloy; primarily of pie or the American football shape of chromium powder, aluminium powder, fusing assistant compacting; it is characterized in that: described chromium powder, aluminium powder are broken under protection of inert gas respectively; also comprise tensio-active agent; the mass percent of each component is respectively: chromium powder 90%-97%, aluminium powder 0-9.48%, fusing assistant 0.01%-5%, tensio-active agent 0.5%-2%; density after each component press forming is: 2.8-5.0g/cm3; wherein
A: the particle size distribution of chromium powder is 10-700 order, wherein 325-700 object chromium powder accounts for the 35%-40% of chromium powder total content, 100-325 object chromium powder accounts for the 40%-45% of chromium powder total content, 60-100 object chromium powder accounts for the 5%-15% of chromium powder total content, 10-60 object chromium powder accounts for the 0-5% of chromium powder total content, and the purity of described chromium metal-powder is more than or equal to 98%;
B: the particle size distribution of aluminium powder is 60-300 order, and the purity of aluminium powder is more than or equal to 98%;
C: fusing assistant particle size distribution is 60-300 order.
Technical solution of the present invention has the following advantages:
In the chromium agent of 1, this programme, the content of chromium powder is high, 90-97% can be reached, when aluminum alloy cast melts, in additive, its Main Function is chromium powder, so when casting molten equivalent aluminium alloy, this programme can add less amount, reaching identical effect, is a kind of impurity after so just energy conservation, and fusing assistant fuses into aluminium liquid, so fusing assistant is fewer, the aluminium alloy quality that casting melts out is better.
2, the particle size distribution due to chromium powder of the present invention is comparatively large, and overall mean particle size is little, just can melt fast at relatively low temperature, when using additive product of the present invention, molten aluminium temperature can be low to moderate 670 DEG C, thus the fuel that can reduce when casting is melted uses, save energy.
3, preparation method of the present invention employs tensio-active agent, on the one hand, tensio-active agent has suspending effect, after using tensio-active agent, even make the product that additive density of the present invention is larger, also suspended state can be in molten aluminium, can not sink to the bottom, in the process melted, additive product can fluctuate in molten aluminium, fusing speed is accelerated, substantially reduce additive and melt the time, in addition, additives suspended is in aluminium liquid, and additive product can fluctuate, thus can make chromium powder dissolve after dispersion evenly; On the other hand, the hydrophobic group of tensio-active agent can by the surface aggregate of metal-powder together, and the chance making metal-powder contact oxygen reduces, thus decreases the formation of chromium metal and aluminum metal oxide film; Again on the one hand due to the polymerization of tensio-active agent, additive product is in state loosely, but can not scatter in transit, such chromium powder and aluminium powder shaping after density can do less, can be dissolved in molten aluminium quickly; The factor of above-mentioned several respects substantially increases the speed of additive melting, and shorten the melting time, the rate of recovery is high.
4, in the present invention, chromium powder size-grade distribution is 10-700 order, and 325-700 object chromium powder accounts for the 35%-40% of chromium powder total content, 100-325 object chromium powder accounts for the 40%-45% of chromium powder total content, the distribution range of chromium powder granularity is very large, after press forming, wrapped up by the chromium powder of smaller particle size completely compared with the chromium powder particle surface of volume particle size, product is added after in aluminium liquid, because the specific surface area of smaller particle size chromium powder is larger, surface energy is large, very fast so heat up, smaller particle size chromium powder is while melting, also transfer heat to the chromium powder particle compared with volume particle size, so just can greatly accelerate to melt compared with the chromium powder of volume particle size, thus shorten the melting time adding the additive of aluminium liquid.
Draw through melting test, the chromium powder rate of recovery of the present invention just can reach 100% at about 10min, and the rate of recovery of chromium powder is very high.
Prioritization scheme 1, to the further optimization of base case, described chromium powder 93%, aluminium powder 3%, fusing assistant 3%, tensio-active agent 1%, the density after above-mentioned composition press forming is 3.7g/cm
3.Contriver finds through test, and the additive product of said ratio and density melts the time, chromium recovery ratio is all more excellent.
Prioritization scheme 2, to the further optimization of base case, described chromium powder 95%, aluminium powder 2%, fusing assistant 1.5%, tensio-active agent 1.5%, the density after above-mentioned composition press forming is 4.1g/cm
3.Contriver finds through test, and the additive product of said ratio and density melts the time, chromium recovery ratio is all more excellent.
Prioritization scheme 3, to the further optimization of base case, described chromium powder 97%, aluminium powder 1%, fusing assistant 0.01%, tensio-active agent 1.99%, the density after above-mentioned composition press forming is 4.8g/cm
3.Contriver finds through test, and the additive product of said ratio and density melts the time, chromium recovery ratio is all more excellent.
Prioritization scheme 4, to the further optimization of base case, any one of prioritization scheme 1,2,3,4, also comprise binding agent, by mass percentage, binding agent accounts for 0-3%.Chromium metal-powder can effectively condense together by binding agent, and be therefore easy to form agglomerating effect, easier compression moulding for the powder that particle diameter is meticulous, the chrome additive of compression moulding can not disperse because particle diameter is meticulous, is convenient to transport; Simultaneously when suppressing, without the need to the too consolidation by chrome additive pressure, under less density, additive is also plastic.After additive is added molten aluminium, density is less can be melted rapidly.
Prioritization scheme 5, to the further optimization of prioritization scheme 4, described binding agent is Polyanionic Cellulose.Contriver finds through test, and when using Polyanionic Cellulose as binding agent, the additive adding molten aluminium can melt from outside to inside gradually, there will not be the phenomenon of aluminium powder scaling loss.
Another object of the present invention is to provide base case one: a kind of preparation method of the chromium agent for the production of aluminium alloy, comprise (1) pulverizing, (2) weighing, (3) mixing, (4) compacting, (5) drying and (6) packaging, in step 1, pulverize under protection of inert gas, the size range choosing chromium powder after pulverizing is 10-700 order, the size-grade distribution of aluminium powder is 40-500 order, and fusing assistant powder size is distributed as 40-500 order; Between step 2 and 3, have additional following steps: according to the quality sum of step 2 weighing gained, take tensio-active agent according to the mass percent of 0.5%-2%, and prepare surfactant soln; The process that step 3 mixes is carried out under the environment of isolated air, and be spilled into by the above-mentioned surfactant soln prepared.
The advantage of above-mentioned preparation method is:
1, the present invention adopts rare gas element to protect when making metal-powder, can effectively prevent metal powder surface from forming oxide film.In addition, the process that step 3 mixes is carried out under the environment of isolated air, can effectively prevent chromium powder, aluminium powder oxidized like this.
2, preparation method of the present invention is by surfactant formulatory forming surfactants solution, and is sprayed in compound, and the content of tensio-active agent is less, surface additive can be made fully to mix with chromium powder, aluminium powder by the mode of spraying.
Prioritization scheme 7, to the further optimization of base case one, between step 2 and 3, also has additional following steps: according to the quality sum of step 2 weighing gained, take binding agent, and be mixed with binder solution according to the mass percent of 0.5%-2%; In the process that step 3 mixes, also the above-mentioned binder solution prepared is spilled into.Binding agent can be made fully to mix with chromium powder, aluminium powder by the mode of spraying.
Embodiment
Tensio-active agent of the present invention is commercially available prod, and classifying type all can not use.Can be stearic acid, Sodium dodecylbenzene sulfonate, glycerin fatty acid ester, polysorbate etc.Tensio-active agent in following embodiment adopts Sodium dodecylbenzene sulfonate.
Fusing assistant of the present invention can be hexafluoro sodium aluminate, sodium-chlor, Repone K, Sodium Fluoride, Potassium monofluoride, sodium sulfate, sodium carbonate etc., and hexafluoro sodium aluminate selected by the fusing assistant in following embodiment.
Shape of product of the present invention can be pie, American football shape, spherical etc., and the result of use of different shape is identical, and the product in following examples is American football shape, and proportioning raw materials, the product index of the product of each embodiment are as shown in the table:
To be described for embodiment 1 below:
Embodiment 1
By the chromium agent of the present embodiment for the production of aluminium alloy, make the American football shape of Φ 16mm*11mm*4mm, by mass percentage, the density after chromium powder 90%, aluminium powder 6%, hexafluoro sodium aluminate 3%, Sodium dodecylbenzene sulfonate 1%, press forming is 2.8g/cm
3.
Above-mentioned additive obtains according to following methods:
(1) pulverize: use rare gas element to protect, chromium metal, aluminum metal and hexafluoro sodium aluminate are pulverized respectively under protection of inert gas, wherein the size range of chromium powder is 10-700 order, the size range of aluminium powder is 40-500 order, and the powder size scope of hexafluoro sodium aluminate is 40-500 order;
Wherein the size-grade distribution of chromium powder is the 35-40% that 325-700 object chromium powder accounts for chromium powder total content, 100-325 object chromium powder accounts for the 35%-45% of chromium powder total content, 60-100 object chromium powder accounts for the 10%-15% of chromium powder total content, and 10-60 object chromium powder accounts for the 0-5% of chromium powder total content; The size-grade distribution of aluminium powder is 50-500 order; The powder size of hexafluoro sodium aluminate is distributed as 50-500 order.Use rare gas element to protect simultaneously, to be combined with oxygen to prevent chromium powder, aluminium powder and hexafluoro sodium aluminate powder and to generate metal oxide film, thus the quality of guarantee chrome additive.
(2) weighing: the chromium powder of step 1 gained, aluminium powder, hexafluoro sodium aluminate powder are carried out weighing according to following weight ratio: chromium powder is 90%, aluminium powder is 6%, hexafluoro sodium aluminate powder be 3%.
(3) prepare Sodium dodecylbenzene sulfonate solution: according to the quality sum of step 2 weighing gained, according to the mass percent preparation Sodium dodecylbenzene sulfonate solution of 1%, the concentration of described Sodium dodecylbenzene sulfonate solution is 30%.
(4) move in mixer by the chromium powder of step 2 gained, aluminium powder and hexafluoro sodium aluminate powder, open mixer according to the rotating speed of 20-30 rev/min, batch mixing 2 minutes, obtains preliminary blended stock, and batch mixing process is also carried out under protection of inert gas.
(5) by the Sodium dodecylbenzene sulfonate spray solution of step 3 gained in the preliminary compound of step 4 gained, open mixer, setting its stirring frequency is 20-30 rev/min, and mixing time is 20 minutes, can obtain the compound powder mixed; After this step, ingredient analysis can be carried out by the sample that is mixed with of extraction 5 different sites, if 5 detected result deviations are in 0.001%, then illustrate and mix, can step 6 be entered, otherwise continue to open mixer, again carry out 20 minutes batch mixings.
(6) compound powder step 5 obtained moves into the spherical press-forming machine of metal-powder, and employing linear pressure is that the pressure of 10 MPas is pressed; The product density of press forming is 2.8g/cm
3.
(7) product that step 6 obtains is put into drying oven dry, make its moisture content lower than 0.2%.
(8) the High Content Chromium additive aluminium foil packing of step 7 gained is finished product.
By the finished product obtained by aforesaid method, adopt nitrogen hydrogen-oxygen determinator to carry out oxygen level test, the result of mensuration is that oxygen level is less than 0.5%.
Embodiment 2
The present embodiment difference from preparation of Example 1 is:
(2) weighing: the chromium powder of step 1 gained, aluminium powder, hexafluoro sodium aluminate powder are carried out weighing according to following weight ratio: chromium powder 98%, hexafluoro sodium aluminate powder 0.01%;
(3) Sodium dodecylbenzene sulfonate solution is prepared: according to the quality sum of step 2 weighing gained, according to the mass percent preparation Sodium dodecylbenzene sulfonate solution of 1.99%;
(6) product density of press forming is 4.8g/cm
3.
Embodiment 5
The present embodiment difference from Example 1 is:
(2) weighing: the chromium powder of step 1 gained, aluminium powder, hexafluoro sodium aluminate powder are carried out weighing according to following mass percent: chromium powder 90%, aluminium powder 4%, hexafluoro sodium aluminate powder 4%.
(3) Sodium dodecylbenzene sulfonate solution is prepared: according to the quality sum of step 2 weighing gained, according to the mass percent preparation Sodium dodecylbenzene sulfonate solution of 1%.
(4) prepare binder solution: according to the quality sum of step 2 weighing gained, according to the mass percent preparation Polyanionic Cellulose solution of 1%, the concentration of described binder solution is 20%.
(6) by the Sodium dodecylbenzene sulfonate solution of step 3 and step 4 gained and Polyanionic Cellulose spray solution in the preliminary compound of step 5 gained, open mixer, setting its stirring frequency is 20-30 rev/min, mixing time is 20 minutes, can obtain the compound powder mixed.
(7) compound powder step 6 obtained moves into press-forming machine, and employing pressure is that the pressure of 10-30 MPa is suppressed, and obtaining density after shaping is 2.8g/cm
3the chromium agent for the production of aluminium alloy.
By the finished product obtained by aforesaid method, adopt nitrogen hydrogen-oxygen determinator to adopt ordinary method to carry out oxygen level test, the result of mensuration is that oxygen level is less than 0.4%.
Moisture content of the present invention is recorded by common aqueous content test method.
The inventive method is owing to have employed Polyanionic Cellulose and Sodium dodecylbenzene sulfonate simultaneously, therefore for the easier polymerization forming of the powder that particle diameter is very thin, can reduce simultaneously metal-powder and oxygen in conjunction with chance, thus the oxygen level of product is reduced, a nearlyer step improves the quality of product of the present invention.
Experiment:
From embodiment 1-5, choose chrome additive (XD) that the Wuxi City Xin Di nonferrous materials company limited that 3 aluminum alloy chromium additives and market buys produces respectively carry out meltings and test, it is put into respectively the aluminium liquid calciner of the plumbago crucible that 3 are used for testing, in the different time periods, the solution in each aluminium liquid melting furnace is sampled, be cooled to after solid until it, dissolved with acid, acid used is concentrated nitric acid and concentration is the mixed in hydrochloric acid of 50%, both volume ratios are 1:1, then the content of chromium in solution is measured with ICP detector, thus obtain the average recovery rate of chromium, wherein, the rate of recovery of chromium refers to that chromium powder is dissolved in the ratio of chromium powder total mass in quality in molten aluminium and additive.The rate of recovery of chromium is higher, illustrates that the amount that in the additive of unit mass, chromium powder melts is more.Table 1, table 2, table 3 are the melting test-results of the rate of recovery of chromium 710 DEG C, 690 DEG C, 670 DEG C time respectively, and concrete outcome is as follows:
Table 1
Table 2
Table 3
Conclusion:
1. under the condition that temperature is identical, the rate of recovery of the chromium of the additive of embodiment 1-5 is obviously high than the rate of recovery of the chrome additive that market is bought (XD), and the time of melting is short.
2. the additive in embodiment of the present invention 1-5 is at the temperature of 670 DEG C, and chromium recovery ratio during 10-15min can reach 95-100%, reaches the highest chromium recovery ratio compared to existing technology during more than 20min, and chromium recovery ratio is higher, melts the time short.
3. the minimum melting temperature (Tm) of additive of the present invention can be low to moderate 670 DEG C, reduces 40 DEG C, greatly saved smelting furnace energy consumption compared to 710 DEG C of prior art.Therefore, the efficiency that chromium agent of the present invention is melted in aluminium liquid is high, and less energy consumption, cost is low.
Claims (8)
1. the chromium agent for the production of aluminium alloy; primarily of pie or the American football shape of chromium powder, aluminium powder, fusing assistant compacting; it is characterized in that: described chromium powder, aluminium powder are broken under protection of inert gas respectively; also comprise tensio-active agent; the mass percent of each component is respectively: chromium powder 90%-97%, aluminium powder 0-9.39%, fusing assistant 0.01%-5%, tensio-active agent 0.5%-2%, and the density after each component press forming is: 2.8-5.0g/cm
3, wherein:
A: the particle size distribution of chromium powder is 10-700 order, wherein 325-700 object chromium powder accounts for the 35%-40% of chromium powder total content, 100-325 object chromium powder accounts for the 40%-45% of chromium powder total content, 60-100 object chromium powder accounts for the 5%-15% of chromium powder total content, 10-60 object chromium powder accounts for the 0-5% of chromium powder total content, and the purity of described chromium metal-powder is more than or equal to 98%;
B: the particle size distribution of aluminium powder is 60-300 order, and the purity of aluminium powder is more than or equal to 98%;
C: fusing assistant particle size distribution is 60-300 order.
2., as claimed in claim 1 for the production of the chromium agent of aluminium alloy, it is characterized in that: described chromium powder 93%, aluminium powder 3%, fusing assistant 3%, tensio-active agent 1%, the density after above-mentioned composition press forming is 3.7g/cm
3.
3., as claimed in claim 1 for the production of the chromium agent of aluminium alloy, it is characterized in that: described chromium powder 95%, aluminium powder 2%, fusing assistant 1.5%, tensio-active agent 1.5%, the density after above-mentioned composition press forming is 4.1g/cm
3.
4., as claimed in claim 1 for the production of the chromium agent of aluminium alloy, it is characterized in that: described chromium powder 97%, aluminium powder 1%, fusing assistant 0.01%, tensio-active agent 1.99%, the density after above-mentioned composition press forming is 4.8g/cm
3.
5. the chromium agent for the production of aluminium alloy as described in any one of claim 1-4, it is characterized in that: also comprise binding agent, by mass percentage, binding agent accounts for 0-3%.
6., as claimed in claim 5 for the production of the chromium agent of aluminium alloy, it is characterized in that: described binding agent is Polyanionic Cellulose.
7. prepare the method for the production of the chromium agent of aluminium alloy described in any one of claim 1-4, comprise (1) pulverizing, (2) weighing, (3) mixing, (4) compacting, (5) drying and (6) packaging, it is characterized in that,
In step 1, be pulverize under protection of inert gas, the size range choosing chromium powder after pulverizing is 10-700 order, and the size-grade distribution of aluminium powder is 40-500 order, and fusing assistant powder size is distributed as 40-500 order;
Between step 2 and 3, have additional following steps: according to the quality sum of step 2 weighing gained, take tensio-active agent according to the mass percent of 0.5%-2%, and prepare surfactant soln;
The process that step 3 mixes is carried out under the environment of isolated air, and be spilled into by the above-mentioned surfactant soln prepared.
8. the method for the chromium agent for the production of aluminium alloy according to claim 7, is characterized in that,
Between step 2 and 3, also have additional following steps: according to the quality sum of step 2 weighing gained, take binding agent according to the mass percent of 0.5%-2%, and be mixed with binder solution;
In the process that step 3 mixes, also the above-mentioned binder solution prepared is spilled into.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105821229A (en) * | 2016-05-27 | 2016-08-03 | 沧州市东众特种合金制造有限公司 | Preparation method for aluminum alloy additive without villiaumite and chlorine salts |
| CN107267787A (en) * | 2017-07-10 | 2017-10-20 | 铜山县丰华工贸有限公司 | A kind of chromium agent and preparation method thereof of aluminum alloy smelting |
| CN113637864A (en) * | 2021-08-17 | 2021-11-12 | 重庆润际远东新材料科技股份有限公司 | Chromium additive for aluminum alloy and preparation method thereof |
| CN114150168A (en) * | 2021-11-20 | 2022-03-08 | 徐州市永晟冶金材料有限公司 | Aluminum alloy metal additive and production method thereof |
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| CN101381821A (en) * | 2008-09-26 | 2009-03-11 | 北京矿冶研究总院 | Flux-free aluminum alloy additive and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105821229A (en) * | 2016-05-27 | 2016-08-03 | 沧州市东众特种合金制造有限公司 | Preparation method for aluminum alloy additive without villiaumite and chlorine salts |
| CN107267787A (en) * | 2017-07-10 | 2017-10-20 | 铜山县丰华工贸有限公司 | A kind of chromium agent and preparation method thereof of aluminum alloy smelting |
| CN113637864A (en) * | 2021-08-17 | 2021-11-12 | 重庆润际远东新材料科技股份有限公司 | Chromium additive for aluminum alloy and preparation method thereof |
| CN114150168A (en) * | 2021-11-20 | 2022-03-08 | 徐州市永晟冶金材料有限公司 | Aluminum alloy metal additive and production method thereof |
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