CN105087975A - High-content titanium additive used for producing aluminum alloy and preparation method of high-content titanium additive - Google Patents
High-content titanium additive used for producing aluminum alloy and preparation method of high-content titanium additive Download PDFInfo
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- CN105087975A CN105087975A CN201510541451.0A CN201510541451A CN105087975A CN 105087975 A CN105087975 A CN 105087975A CN 201510541451 A CN201510541451 A CN 201510541451A CN 105087975 A CN105087975 A CN 105087975A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000010936 titanium Substances 0.000 title claims abstract description 125
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 125
- 239000000654 additive Substances 0.000 title claims abstract description 63
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 35
- 230000000996 additive effect Effects 0.000 title abstract description 40
- 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 66
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 62
- 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 59
- 239000000843 powder Substances 0.000 claims description 56
- -1 by mass percentage Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000013543 active substance Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 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 23
- 230000008018 melting Effects 0.000 abstract description 23
- 238000011084 recovery Methods 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 229910045601 alloy Inorganic materials 0.000 description 22
- 239000000956 alloy Substances 0.000 description 22
- 229910001388 sodium aluminate Inorganic materials 0.000 description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 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
- 238000005275 alloying Methods 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 238000012913 prioritisation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000005457 optimization Methods 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
- 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 6
- 238000005266 casting Methods 0.000 description 5
- 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
- 238000000748 compression moulding Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 239000002253 acid Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000004907 flux Effects 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
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 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
- 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
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material 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
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method 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
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the field of additives of aluminum alloy, and discloses a high-content titanium additive used for producing aluminum alloy and a preparation method of the high-content titanium additive. The high-content titanium additive is shaped like a cake or a rugby ball mainly formed by pressing titanium powder, aluminum power and a fluxing agent. The titanium powder and the aluminum powder are smashed under the protection of inert gas. The high-content titanium additive further comprises a surface active agent. The mass percentage of the titanium powder is 85%-95%. The mass percentage of the aluminum powder is 4%-14.49%. The mass percentage of the fluxing agent is 0.01%-5%. The mass percentage of the surface active agent is 0.5%-2%. The titanium metal element content of the additive can reach up to 95% at most. The melting temperature of the titanium additive is low, the additive can be melted in molten aluminum under the temperature lowered to 670 DEG C or lower, the melting time is short, melting can be achieved within 10-15 minutes, and the recovery rate of titanium metal elements reaches up to 98% or above.
Description
Technical field
The invention belongs to the additive agent field of aluminium alloy, be specifically related to a kind of aluminium alloy titanium 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, be eliminated gradually, people start to adopt and metal-powder and fusing assistant are fully mixed the mode added in molten aluminium after compression moulding carry out the alloying of metal in recent years.During enforcement, the temperature of aluminum alloy melt casting is generally about 710 DEG C, directly adds in aluminium liquid and can melt with the form of elemental metals powder for low melting point or the large alloying element of melting degree, but for manganese, iron, chromium, the high-melting-points such as titanium 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, chromium, the temperature of titanium metal, then the aluminium liquid in smelting furnace just can gasify, and therefore solution is at the temperature that can not gasify at aluminium, fast by manganese, iron, chromium, the metals such as titanium melt, and in order to reach this object, people have expected manganese, iron, chromium, titanium valve is broken, and adds fusing assistant in the powder, and makes solid shape, i.e. our usually said manganese agent, chalybeate, chromium agent, titanium agent, when by manganese agent, chalybeate, chromium agent, titanium agent is put in aluminium liquid smelting furnace, and fusing assistant reacts rapidly in aluminium liquid, and the heat of generation can reach and make manganese within for some time, iron, chromium, the temperature that the metals such as titanium melt, thus reach melting.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 or titanium is the highest can only reach about 85%, if the content of the manganese in additive product, iron, chromium or titanium 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 or titanium can not melt completely; 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, have following problem, for titanium additives: 1, melt relatively slower, the melting time is generally more than 20min, melts the time long; 2, the additive adding molten aluminium easily sinks to the bottom, once sink to the bottom, titanium valve fusing speed can be caused to slow down on the one hand, and after titanium valve can be caused on the other hand to dissolve, dispersion is uneven; 3, 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 high-content titanium additives for the production of aluminium alloy that the time is short, titanium recovery rate is high.
The object of the present invention is to provide following base case: a kind of high-content titanium additives for the production of aluminium alloy; primarily of pie or the American football shape of titanium valve, aluminium powder, fusing assistant compacting; described titanium valve, aluminium powder are broken under protection of inert gas respectively; also comprise tensio-active agent, the mass percent of each component is respectively: titanium valve 85%-95%, aluminium powder 4%-14.49%, fusing assistant 0.01%-5%, tensio-active agent 0.5%-2%.
Technical solution of the present invention has the following advantages:
1. in additive, the content of titanium valve is high, and at least more than 90%, when aluminum alloy cast melts, in titanium agent, its Main Function is titanium valve, so when casting molten equivalent aluminium alloy, this programme can add less amount, reaches identical effect, and so just can conservation.
2. fusing assistant is introduced as impurity, and this programme flux content used is very low, so greatly reduce the foreign matter content in aluminium alloy.
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 titanium valve 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 titanium 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 titanium valve 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.
Draw through melting test, the titanium valve rate of recovery of the present invention just can reach 100% at about 10min, and the rate of recovery of titanium valve is very high.
Prioritization scheme 1, to the further optimization of base case, described titanium valve 90%, aluminium powder 5%, fusing assistant 3%, tensio-active agent 2%.Contriver finds through test, and the additive product of said ratio melts the time, titanium recovery rate is all more excellent.
Prioritization scheme 2, to the further optimization of base case, described titanium valve 95%, aluminium powder 4%, fusing assistant 0.1%, tensio-active agent 0.99%.Contriver finds through test, and the additive product of said ratio melts the time, titanium recovery rate is all more excellent.
Prioritization scheme 3, to the further optimization of base case, the density range after each composition press forming is: 2.6-3.5g/cm
3.Contriver finds through test, and the additive product being pressed into above-mentioned density melts the time, titanium recovery rate 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%.Titanium 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 titanium additives 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 titanium additives 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 titanium valve scaling loss.
Prioritization scheme 5, to the further optimization of base case, the size-grade distribution of described titanium valve is: 325-700 object titanium valve accounts for the 35%-40% of titanium valve total content, 100-325 object titanium valve accounts for the 40%-45% of titanium valve total content, 60-100 object titanium valve accounts for the 5%-10% of titanium valve total content, and 10-60 object titanium valve accounts for the 0-5% of titanium valve total content.As everyone knows, granularity is less, more easily melts, and the size-grade distribution in this programme can make additive be dissolved in rapidly in molten aluminium.
Another object of the present invention is to provide base case one: a kind of preparation method of the high-content titanium additives 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 titanium valve 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 titanium valve, 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 titanium valve, 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 titanium valve, aluminium powder by the mode be spilled into.
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 high-content titanium additives 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 titanium valve 85%, aluminium powder 10%, hexafluoro sodium aluminate 3%, Sodium dodecylbenzene sulfonate 2%, press forming is 2.6g/cm
3.
Above-mentioned additive obtains according to following methods:
(1) pulverize: use rare gas element to protect, titanium metal, aluminum metal and hexafluoro sodium aluminate are pulverized respectively under protection of inert gas, wherein the size range of titanium valve 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 titanium valve is the 35-40% that 325-700 object titanium valve accounts for titanium valve total content, 100-325 object titanium valve accounts for the 35%-45% of titanium valve total content, 60-100 object titanium valve accounts for the 10%-15% of titanium valve total content, and 10-60 object titanium valve accounts for the 0-5% of titanium valve 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 titanium valve, aluminium powder and hexafluoro sodium aluminate powder and to generate metal oxide film, thus the quality of guarantee titanium additives.
(2) weighing: the titanium valve of step 1 gained, aluminium powder, hexafluoro sodium aluminate powder are carried out weighing according to following weight ratio: titanium valve is 85%, aluminium powder is 10%, 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 2%, the concentration of described Sodium dodecylbenzene sulfonate solution is 30%.
(4) move in mixer by the titanium valve 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 2.6g/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 titanium additives 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 titanium valve of step 1 gained, aluminium powder, hexafluoro sodium aluminate powder are carried out weighing according to following weight ratio: titanium valve 90%, aluminium powder 5%, hexafluoro sodium aluminate powder 3%;
(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 2%;
(6) product density of press forming is 3.0g/cm
3.
Embodiment 5
The present embodiment difference from Example 1 is:
(2) weighing: the titanium valve of step 1 gained, aluminium powder, hexafluoro sodium aluminate powder are carried out weighing according to following mass percent: titanium valve 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 3.4g/cm
3the high-content titanium additives 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:
Melting test is carried out in the titanium agent (75Ti) choosing the Wuyi Hong Rui metallic substance company limited that 3 aluminium alloy titanium additives and market are bought respectively from embodiment 1-5, 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 titanium in solution is measured with ICP detector, thus obtain the average recovery rate of titanium, wherein, the rate of recovery of titanium refers to that titanium valve is dissolved in the ratio of titanium valve total mass in quality in molten aluminium and additive.The rate of recovery of titanium is higher, illustrates that the amount that in the additive of unit mass, titanium valve melts is more.Table 1, table 2, table 3 are the melting test-results of the rate of recovery of titanium 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 titanium of the additive of embodiment 1-5 is obviously high than the rate of recovery of the titanium agent (75Ti) that market is bought, 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 titanium recovery rate during 10-15min can reach 95-100%, reaches the highest titanium recovery rate compared to existing technology during more than 20min, and titanium recovery rate 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 titanium agent of the present invention is melted in aluminium liquid is high, and less energy consumption, cost is low.
Claims (9)
1. the high-content titanium additives for the production of aluminium alloy; primarily of pie or the American football shape of titanium valve, aluminium powder, fusing assistant compacting; it is characterized in that: described titanium valve, aluminium powder are broken under protection of inert gas respectively; also comprise tensio-active agent, the mass percent of each component is respectively: titanium valve 85%-95%, aluminium powder 4%-14.49%, fusing assistant 0.01%-5%, tensio-active agent 0.5%-2%.
2., as claimed in claim 1 for the production of the high-content titanium additives of aluminium alloy, it is characterized in that: described titanium valve 90%, aluminium powder 5%, fusing assistant 3%, tensio-active agent 2%.
3., as claimed in claim 1 for the production of the high-content titanium additives of aluminium alloy, it is characterized in that: described titanium valve 95%, aluminium powder 4%, fusing assistant 0.1%, tensio-active agent 0.99%.
4., as claimed in claim 1 for the production of the high-content titanium additives of aluminium alloy, it is characterized in that: the density range after each composition press forming is: 2.6-3.5g/cm
3.
5. the high-content titanium additives 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 high-content titanium additives of aluminium alloy, it is characterized in that: described binding agent is Polyanionic Cellulose.
7. as claimed in claim 1 for the production of the high-content titanium additives of aluminium alloy, it is characterized in that: the size-grade distribution of described titanium valve is: 325-700 object titanium valve accounts for the 35%-40% of titanium valve total content, 100-325 object titanium valve accounts for the 40%-45% of titanium valve total content, 60-100 object titanium valve accounts for the 5%-10% of titanium valve total content, and 10-60 object titanium valve accounts for the 0-5% of titanium valve total content.
8. prepare the method for the production of the high-content titanium additives 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 titanium valve 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.
9. the method for the high-content titanium additives for the production of aluminium alloy according to claim 8, 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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| 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 |
| CN106756179A (en) * | 2016-12-03 | 2017-05-31 | 沧州东盛金属添加剂制造有限公司 | A kind of titanium additives and preparation method thereof |
| CN108754201A (en) * | 2018-05-28 | 2018-11-06 | 沧州东盛金属添加剂制造有限公司 | Composite solvent type additive |
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| CN101597700A (en) * | 2009-07-02 | 2009-12-09 | 河北工业大学 | The additive and the methods for making and using same thereof that are used for smelting aluminium alloy |
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| CN101597700A (en) * | 2009-07-02 | 2009-12-09 | 河北工业大学 | The additive and the methods for making and using same thereof that are used for smelting aluminium alloy |
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| 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 |
| CN106756179A (en) * | 2016-12-03 | 2017-05-31 | 沧州东盛金属添加剂制造有限公司 | A kind of titanium additives and preparation method thereof |
| CN108754201A (en) * | 2018-05-28 | 2018-11-06 | 沧州东盛金属添加剂制造有限公司 | Composite solvent type additive |
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