CA2051605A1 - Method and apparatus for production of metal base composite material - Google Patents
Method and apparatus for production of metal base composite materialInfo
- Publication number
- CA2051605A1 CA2051605A1 CA002051605A CA2051605A CA2051605A1 CA 2051605 A1 CA2051605 A1 CA 2051605A1 CA 002051605 A CA002051605 A CA 002051605A CA 2051605 A CA2051605 A CA 2051605A CA 2051605 A1 CA2051605 A1 CA 2051605A1
- Authority
- CA
- Canada
- Prior art keywords
- particles
- molten metal
- crucible
- metal
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 73
- 239000002184 metal Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims abstract description 129
- 239000007787 solid Substances 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 20
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 150000002739 metals Chemical class 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 238000013019 agitation Methods 0.000 claims abstract description 12
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 7
- 230000005593 dissociations Effects 0.000 claims abstract description 7
- 238000009827 uniform distribution Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 43
- 239000010953 base metal Substances 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 34
- 239000000956 alloy Substances 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 150000001247 metal acetylides Chemical class 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000000859 sublimation Methods 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 description 37
- 239000000155 melt Substances 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000003014 reinforcing effect Effects 0.000 description 9
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012763 reinforcing filler Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910010039 TiAl3 Inorganic materials 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- -1 borides Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910016459 AlB2 Inorganic materials 0.000 description 1
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910001141 Ductile iron Inorganic materials 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- RRCYYLHJWRYWEI-UHFFFAOYSA-N OOOOOOOOOOOOOOOOOOOOO Chemical compound OOOOOOOOOOOOOOOOOOOOO RRCYYLHJWRYWEI-UHFFFAOYSA-N 0.000 description 1
- 238000004616 Pyrometry Methods 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- 101000693961 Trachemys scripta 68 kDa serum albumin Proteins 0.000 description 1
- OQPDWFJSZHWILH-UHFFFAOYSA-N [Al].[Al].[Al].[Ti] Chemical compound [Al].[Al].[Al].[Ti] OQPDWFJSZHWILH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 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 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000004157 plasmatron Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001303 quality assessment method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910021324 titanium aluminide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/06—Alloys
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D3/18—Charging particulate material using a fluid carrier
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Engineering & Computer Science (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method of making a composite material consists of entraining finely divided solid additive particles in a stream of ionized inert gas and ionizing the inert gas and utilizing heat generated by the ionized gas to heat the solid particles to a high temperature which is less than the temperature in at which the solid particles become non-solid due to melting sublimination or dissociation. Then, injecting the stream of gas and entrained heated solid particles into a molten metal mass to provide a mixture of finely divided solid particles and molten metal and thereafter causing physical agitation of the mixture of molten metal and solid particles to establish a substantially uniform distribution of solid particles in the molten metal. Such physical agitation of molten metal is continued until the mixture of finely divided particles and metals is completely solidified.
A method of making a composite material consists of entraining finely divided solid additive particles in a stream of ionized inert gas and ionizing the inert gas and utilizing heat generated by the ionized gas to heat the solid particles to a high temperature which is less than the temperature in at which the solid particles become non-solid due to melting sublimination or dissociation. Then, injecting the stream of gas and entrained heated solid particles into a molten metal mass to provide a mixture of finely divided solid particles and molten metal and thereafter causing physical agitation of the mixture of molten metal and solid particles to establish a substantially uniform distribution of solid particles in the molten metal. Such physical agitation of molten metal is continued until the mixture of finely divided particles and metals is completely solidified.
Description
2~51~
ME~OD AND APPARATUS FOR PRODUCTION OF NETAL BASE
COMPOSIT~ NA~E~IAL
FIELD OF TH~ INVEN~ION
The present invention relates to the metallurgical field, and more specifically to a method for the production of cast base metal material having distributed therein very fine particles which can be particles of ceramics, metals, alloys, intermetallics, carbides, nitrides, borides and substances useful in enhancing properties of the base metal.
BACKGROUND OF THE INVENTION
Development of the aircraft and ship building, car making and a number of other industries require new materials having improved workability and service properties.
Metal~ic structural materials (alloys) are nowadays produced by melting the base metal to li~uid form with additive components, with the melting process going at the temperature of the entire system which ensures the complete melting and mutual dissolution of the components (Fig. 2a).
With the drop of temperature of the alloy during cooling and solidification, the solubility of the alloy components sharply decreases and, at a certain temperature particular for each alloy system and composition, solid phases begin to precipitate and grow from the homogeneous melt in the form of alloy component crystals, , 20~160~
or, more frequently, in the form of the crystals of the chemical compounds of components (intermetallic phases) (Fig. 2, b,c). With further cooling the rest of the melt is crystallized in the form of a solid solution of the components in the base metal (Fig. 2, d).
Intermetallic phases with crystal lattice and properties different from those of the base alloy (matrix) strongly affect the properties of the alloy system as a whole.
The size of the intermetallic phases precipitated in the process of crystallization of the alloy should not exceed fractions of one micron, otherwise guality of the alloy will be sharply impaired due to loss of ductility and strength.
The solubility of metals and metalloids in the metallic matrix is very much limited in the solid state and this factor accounts for the narrow selection of commercial alloys and the practically achieved limit of improvement in the properties of the commercial structural alloys by change in composition.
A new class of structural materials have been developed, which contain artificially incorporated particles or fibers of oxides, carbides and other compounds enabling the attainment of assured properties of the system as a whole. Such materials are ~nown as composites since the components of the metallic system are not precipitated from the matrix metal, as is the case with the conventional alloys, but are artificially incorporated into the system. All known metallic alloys representing the matrix with incorporated particles, whose properties significantly differ from the matrix, are basically the composites, although of natural ' .: , `` 20~160~
occurrence in the making of the alloy.
The properties of metallic materials represented by a composite system of artificial or natural origin are indicated as follows:
- ductility of the material is determined by ability of the matrix (as a rule the ability of the solid solutions of components in the base alloy) for plastic flow, as well as by size and syngonia (crystalline structure) of intermetalloid and other inclusions in the matrix);
- strength, heat resistance, fatigue strength, resistance of materials to development of cracks is determined by interaction of the of the inclusions and the matrix, as well as distortions of the crystalline lattice of the matrix under action of inclusions;
- hardness, wear resistance, tribotechnical properties of the material are determined by properties of the inclusions:
- modulus of elasticity, linear expansion factor, specific weight (density) of the material are determined by a set of properties of the matrix and inclusions.
Thus, the development of new metallic materials with a predetermined combination of workability and service properties should be theoretically achievable on the basis of selection of the optimum composition of the metallic system in each case, that is selection of the matrix and inclusions whosé properties and interaction determine the properties of the composite system as a whole.
Selection of the metallic system base (matrix) is determined by required service properties of the material and level of its : .:
.
. . - .
.
. .
,1 .
'. -' ~ ' ' ' 2~5160~
properties (steel, aluminum, copper, magnesium, nickel, etc.).
The major difficulty in implementation of the technology for production of structural metallic materials is the injection of components into the structure in the form of superfine particles of compounds thermodynamically and thermally stable in the matrix, and which measure from a few nanometres to a few microns.
In the production of natural composite metallic materials (i.e. complex alloys) this problem is dealt with by precipitation of particles (intermetalloids) from supersaturated solid solutions of the components of the alloy in the base metal produced by the use of high-rate cooling of homogeneous melts. The required cooling rate can be practically achieved only in case of relatively small quantities of alloy melt. In practice, a high cooling rate is provided by physical dispersion of the melt followed by cooling fine drops of the melt in a cooling medium. This requires expensive operations of drying, degassing and compacting particles (granules) to provide pellets. Thus, the technology for production of new metallic alloys by the pelletizing technique has not found wide use in the industry.
The difficulty of introducing superfine particles into the metallic melts in attributed to two circumstances. First due to lack of fluidity of superfine particles (thousandths of microns or less in size) the metering of particles when injected into the melt is rather difficult or sometimes even impossible. Second, due to presence of adsorbed oxygen on the surface of the particles upon in contact with the melt, oxides of the base metal are formed on the " , . .
, 2~5160~
surface, which prohibits wetting of the particles by the melt.
This problem especially manifests itself during injection of the particles into the melts of metals having high oxygen reactivity (aluminum, magnesium, etc.). The above factor also inhibits implementation of such techniques as the direct modification of the alloys by injection of particles - crystallization nuclei into the melt, alloying the melts by injection of alloy components in the form of the powder, use of powdered waste of alloying materials (eg. silicon) in production of alloys, in particular those of aluminum-silicon system.
One of the most important features of the proposed technology and devices for its implementation is the possibility of injection into the melt of fine particles of the filler materials (in case of production of composites) or structural components (in case of production of alloys), with the formation of the alloy structure following the scheme shown in Fig. 3.
The matrix free from the atoms of the component is injected with particles of a desired filler material ~Fig. 3a). When equilibrium of the system exists between the structural component ~Ax 13y) and solution of the alloy component B in the matrix A, particles incorporated into the matrix dissolve to the concentration of saturation at the appropriate temperature with the decrease in size, this process is highly controllable and enables production of alloys with structure with alloy a predetermined component of limited solubility.
Major stages of a process for the production of cast composite ,.. ,..... - . . ~ :
. ; ' ' .
20~60a materials involved are described in "Solidification, Structures and Properties of Cast Metal-Ceramic Particle Composites" - Rohatgi P.K., Asthana R., Das S. - Inst. Metal Rev., - 1986 - Vol. 31, N3 -pp. 15-139 and include:
- production of the basic melt;
- uniform distribution of solid particles in a mass molten metal;
- crystallization of the resultant composite material.
The following methods have been used in the prior art for injection of superfine particles into a melt as described in "Cast Aluminum-Graphite Particle Composites - a Potential Engineering Material" - Rohatgi P.K., Das S.-, Dan T. K. - J. Inst. Eng., -March, 1989 - Vol. 67, N2 - pp. 77-83:
- mechanical stirring of the melt and added particles;
- pressing pellets mixed powered matrix metals and reinforcing particles followed by plunging the particles to the melt and mechanical stirring of the melt;
- dispersion of particles in melt by ultrasound irradiation.
Problems encountered in the production of cast metal composites relate to lack of or low wetability of the reinforcing filler particles with the matrix melt, as well as non-uniformity of the cast material due to large differences in densities between the matrix and the filler material.
2~160~
Increase in the strength of the bond between the reinforcing filler particles and the base metal matrix is achieved by a number of techniques as described in "Wetability of Graphite to Liquid Aluminum and the Effect of alloying Elements on It", Choh Takao, Kemmel Roland, Oki Takeo - Z. Metallklunde" - 1987 - Vol.
78, N4 - pp. 286-290, i.e.:
- application of metal-philic coatings on the ; surface of the reinforcing filler particles;
- introduction of surfactants into the base metal melt;
- increase of the melt temperature.
There is also known a method for production of composites (Application No. 56-141960, Japan, dated 08.04.80 (No. 55-45955), published 05.11.81) in which is suggested the use as a filler of natural hollow microspheres 150 micron in diameter sufficiently compatible with various metallic materials, as well as graphite powders, TiB2, aluminum nitride and oxide, flaky and chipped graphite and calcium metal is added to the melt in quantity of 0.05-5.0 wt.~ to ensure uniformity of materials.
~ he major disadvantage of this method is the necessity for introduction into the melt of an element (calcium) which is soluble in the li~uid base metal, but practically insoluble in the case solid matrix and which forms a brittle eutectic component w'ith the matrix. This results in lowered mechanical properties of the matrix and of the composite itself. Besides, the use, as a filler, o~ hollow microspheres of the recited sizes (150 micron) does not ::, - ~ , , 20~60~
help to improve absolute values of mechanical properties and can result only in some improvement in their relative values per unit of mass.
Prior art relevant to the present invention is the method for production of composite materials (Met. Trans., 1978, v. 9 N 3, pp. 383-388) using the base molten metals - Mg. Al, Fe, Ni, Cr, Co doped with insoluble oxide particles (Al203, BeO,CaO, CeO2, TiO2~
MgO, ThO2, VO2, ZrO2), carbides, borides, nitrides of Nb, Ta, Hf, Ti, Zr sized 0.01-10 micron. The particles are injected as powder or thin fibers. To ensure uniform distribution of the particles in the melt they are injected in a stream of preheated inert gas (Ar, He) while vigorously stirring the base metal. Volume percentage of particles may range from 0.5 to 20%. Also one of the elements which improve the surface activity at the interface the particle-melt is injected into the molten metal. Injection of such surface active metals (Mg, Si, Ti, Zr, V, Nb) ensures formation of a metal-philic casing on the oxides which significantly improves d, wetability in the system and there is no segregation in the melt over a period of 30 min.
The foregoing method has the following disadvantages:
1) the chemical composition of the matrix melt is limited by need to inject surface ac,tive metals which in a number of cases may lead to impairment of technological and mechanical properties of the resulting composite material:
2) the absence of stirring in the course of solidification promotes, especially in case of a long , ' ; . , ': . , , ~,:
- ~ .
~0~160~
solidification time, the formation of segregated and laminated areas, and consequently quality of the resulting composite material is lowered;
ME~OD AND APPARATUS FOR PRODUCTION OF NETAL BASE
COMPOSIT~ NA~E~IAL
FIELD OF TH~ INVEN~ION
The present invention relates to the metallurgical field, and more specifically to a method for the production of cast base metal material having distributed therein very fine particles which can be particles of ceramics, metals, alloys, intermetallics, carbides, nitrides, borides and substances useful in enhancing properties of the base metal.
BACKGROUND OF THE INVENTION
Development of the aircraft and ship building, car making and a number of other industries require new materials having improved workability and service properties.
Metal~ic structural materials (alloys) are nowadays produced by melting the base metal to li~uid form with additive components, with the melting process going at the temperature of the entire system which ensures the complete melting and mutual dissolution of the components (Fig. 2a).
With the drop of temperature of the alloy during cooling and solidification, the solubility of the alloy components sharply decreases and, at a certain temperature particular for each alloy system and composition, solid phases begin to precipitate and grow from the homogeneous melt in the form of alloy component crystals, , 20~160~
or, more frequently, in the form of the crystals of the chemical compounds of components (intermetallic phases) (Fig. 2, b,c). With further cooling the rest of the melt is crystallized in the form of a solid solution of the components in the base metal (Fig. 2, d).
Intermetallic phases with crystal lattice and properties different from those of the base alloy (matrix) strongly affect the properties of the alloy system as a whole.
The size of the intermetallic phases precipitated in the process of crystallization of the alloy should not exceed fractions of one micron, otherwise guality of the alloy will be sharply impaired due to loss of ductility and strength.
The solubility of metals and metalloids in the metallic matrix is very much limited in the solid state and this factor accounts for the narrow selection of commercial alloys and the practically achieved limit of improvement in the properties of the commercial structural alloys by change in composition.
A new class of structural materials have been developed, which contain artificially incorporated particles or fibers of oxides, carbides and other compounds enabling the attainment of assured properties of the system as a whole. Such materials are ~nown as composites since the components of the metallic system are not precipitated from the matrix metal, as is the case with the conventional alloys, but are artificially incorporated into the system. All known metallic alloys representing the matrix with incorporated particles, whose properties significantly differ from the matrix, are basically the composites, although of natural ' .: , `` 20~160~
occurrence in the making of the alloy.
The properties of metallic materials represented by a composite system of artificial or natural origin are indicated as follows:
- ductility of the material is determined by ability of the matrix (as a rule the ability of the solid solutions of components in the base alloy) for plastic flow, as well as by size and syngonia (crystalline structure) of intermetalloid and other inclusions in the matrix);
- strength, heat resistance, fatigue strength, resistance of materials to development of cracks is determined by interaction of the of the inclusions and the matrix, as well as distortions of the crystalline lattice of the matrix under action of inclusions;
- hardness, wear resistance, tribotechnical properties of the material are determined by properties of the inclusions:
- modulus of elasticity, linear expansion factor, specific weight (density) of the material are determined by a set of properties of the matrix and inclusions.
Thus, the development of new metallic materials with a predetermined combination of workability and service properties should be theoretically achievable on the basis of selection of the optimum composition of the metallic system in each case, that is selection of the matrix and inclusions whosé properties and interaction determine the properties of the composite system as a whole.
Selection of the metallic system base (matrix) is determined by required service properties of the material and level of its : .:
.
. . - .
.
. .
,1 .
'. -' ~ ' ' ' 2~5160~
properties (steel, aluminum, copper, magnesium, nickel, etc.).
The major difficulty in implementation of the technology for production of structural metallic materials is the injection of components into the structure in the form of superfine particles of compounds thermodynamically and thermally stable in the matrix, and which measure from a few nanometres to a few microns.
In the production of natural composite metallic materials (i.e. complex alloys) this problem is dealt with by precipitation of particles (intermetalloids) from supersaturated solid solutions of the components of the alloy in the base metal produced by the use of high-rate cooling of homogeneous melts. The required cooling rate can be practically achieved only in case of relatively small quantities of alloy melt. In practice, a high cooling rate is provided by physical dispersion of the melt followed by cooling fine drops of the melt in a cooling medium. This requires expensive operations of drying, degassing and compacting particles (granules) to provide pellets. Thus, the technology for production of new metallic alloys by the pelletizing technique has not found wide use in the industry.
The difficulty of introducing superfine particles into the metallic melts in attributed to two circumstances. First due to lack of fluidity of superfine particles (thousandths of microns or less in size) the metering of particles when injected into the melt is rather difficult or sometimes even impossible. Second, due to presence of adsorbed oxygen on the surface of the particles upon in contact with the melt, oxides of the base metal are formed on the " , . .
, 2~5160~
surface, which prohibits wetting of the particles by the melt.
This problem especially manifests itself during injection of the particles into the melts of metals having high oxygen reactivity (aluminum, magnesium, etc.). The above factor also inhibits implementation of such techniques as the direct modification of the alloys by injection of particles - crystallization nuclei into the melt, alloying the melts by injection of alloy components in the form of the powder, use of powdered waste of alloying materials (eg. silicon) in production of alloys, in particular those of aluminum-silicon system.
One of the most important features of the proposed technology and devices for its implementation is the possibility of injection into the melt of fine particles of the filler materials (in case of production of composites) or structural components (in case of production of alloys), with the formation of the alloy structure following the scheme shown in Fig. 3.
The matrix free from the atoms of the component is injected with particles of a desired filler material ~Fig. 3a). When equilibrium of the system exists between the structural component ~Ax 13y) and solution of the alloy component B in the matrix A, particles incorporated into the matrix dissolve to the concentration of saturation at the appropriate temperature with the decrease in size, this process is highly controllable and enables production of alloys with structure with alloy a predetermined component of limited solubility.
Major stages of a process for the production of cast composite ,.. ,..... - . . ~ :
. ; ' ' .
20~60a materials involved are described in "Solidification, Structures and Properties of Cast Metal-Ceramic Particle Composites" - Rohatgi P.K., Asthana R., Das S. - Inst. Metal Rev., - 1986 - Vol. 31, N3 -pp. 15-139 and include:
- production of the basic melt;
- uniform distribution of solid particles in a mass molten metal;
- crystallization of the resultant composite material.
The following methods have been used in the prior art for injection of superfine particles into a melt as described in "Cast Aluminum-Graphite Particle Composites - a Potential Engineering Material" - Rohatgi P.K., Das S.-, Dan T. K. - J. Inst. Eng., -March, 1989 - Vol. 67, N2 - pp. 77-83:
- mechanical stirring of the melt and added particles;
- pressing pellets mixed powered matrix metals and reinforcing particles followed by plunging the particles to the melt and mechanical stirring of the melt;
- dispersion of particles in melt by ultrasound irradiation.
Problems encountered in the production of cast metal composites relate to lack of or low wetability of the reinforcing filler particles with the matrix melt, as well as non-uniformity of the cast material due to large differences in densities between the matrix and the filler material.
2~160~
Increase in the strength of the bond between the reinforcing filler particles and the base metal matrix is achieved by a number of techniques as described in "Wetability of Graphite to Liquid Aluminum and the Effect of alloying Elements on It", Choh Takao, Kemmel Roland, Oki Takeo - Z. Metallklunde" - 1987 - Vol.
78, N4 - pp. 286-290, i.e.:
- application of metal-philic coatings on the ; surface of the reinforcing filler particles;
- introduction of surfactants into the base metal melt;
- increase of the melt temperature.
There is also known a method for production of composites (Application No. 56-141960, Japan, dated 08.04.80 (No. 55-45955), published 05.11.81) in which is suggested the use as a filler of natural hollow microspheres 150 micron in diameter sufficiently compatible with various metallic materials, as well as graphite powders, TiB2, aluminum nitride and oxide, flaky and chipped graphite and calcium metal is added to the melt in quantity of 0.05-5.0 wt.~ to ensure uniformity of materials.
~ he major disadvantage of this method is the necessity for introduction into the melt of an element (calcium) which is soluble in the li~uid base metal, but practically insoluble in the case solid matrix and which forms a brittle eutectic component w'ith the matrix. This results in lowered mechanical properties of the matrix and of the composite itself. Besides, the use, as a filler, o~ hollow microspheres of the recited sizes (150 micron) does not ::, - ~ , , 20~60~
help to improve absolute values of mechanical properties and can result only in some improvement in their relative values per unit of mass.
Prior art relevant to the present invention is the method for production of composite materials (Met. Trans., 1978, v. 9 N 3, pp. 383-388) using the base molten metals - Mg. Al, Fe, Ni, Cr, Co doped with insoluble oxide particles (Al203, BeO,CaO, CeO2, TiO2~
MgO, ThO2, VO2, ZrO2), carbides, borides, nitrides of Nb, Ta, Hf, Ti, Zr sized 0.01-10 micron. The particles are injected as powder or thin fibers. To ensure uniform distribution of the particles in the melt they are injected in a stream of preheated inert gas (Ar, He) while vigorously stirring the base metal. Volume percentage of particles may range from 0.5 to 20%. Also one of the elements which improve the surface activity at the interface the particle-melt is injected into the molten metal. Injection of such surface active metals (Mg, Si, Ti, Zr, V, Nb) ensures formation of a metal-philic casing on the oxides which significantly improves d, wetability in the system and there is no segregation in the melt over a period of 30 min.
The foregoing method has the following disadvantages:
1) the chemical composition of the matrix melt is limited by need to inject surface ac,tive metals which in a number of cases may lead to impairment of technological and mechanical properties of the resulting composite material:
2) the absence of stirring in the course of solidification promotes, especially in case of a long , ' ; . , ': . , , ~,:
- ~ .
~0~160~
solidification time, the formation of segregated and laminated areas, and consequently quality of the resulting composite material is lowered;
3) insolubility of the reinforcing particles excludes the possibility of using this method for production of materials with the matrix reinforced with superfine particles of those elements or their compounds which are traditional strengtheners in production of materials by joint crystallization of the base metal with alloying additives and subsequent thermo-mechanical working.
SUM~ARY OF THE INVENTION
An object of the present invention is improvement in quality of composite materials by increasinq the uniformity of dispersion of reinforcing filler particles and the strength of their adhesion with the base metal matrix and the ability to provide an expanded group of composite materials by the use of a wide range of ceramic particles, metals and intermetallics including carbides, nitrides, borides, oxides, graphite and glasses.
The foregoing object and other objects are achieved by a method o~ making composite materials which includes the steps of entraining finely divided solid additive particles, e.g. of a ceramic, metal, lntermetallic including oxides, borides, carbides, nitrides, graphite, glasses in an inert gas and ionizing the entraining inert gas t~ heat the solid particles to a high temperature which is less than the temperature at which the particles become non-solid due to melting, sublimation, or dissociation, but more than about 1/2 of such temperature, and 2~5160~
injecting a stream of the ionized entraining gas and entrained heated solid particles into a molten metal mass while maintaining a stirring movement in the mass of molten metal sufficient to promote and to maintain dispersion of the added particles to solidify in a composite mass while maintaining a stirring movement in the solid particle-containing molten metal until solidification thereof is complete.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1, 4 and 5 show apparatus for the practice of various embodiments of the invention: and Figures 2 and 3 are representations of metallurgical conditions which occur in the course of alloy formation.
DETAlLED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the practice of the present invention, the base metal melt can be aluminum, iron, copper, magnesium, nickel, cobalt, chromium.
Suitable base metals are alloys of the above-mentioned metals in which they are the predominant constituent, such as aluminum containing up to 40~ by weight manganese, and steels, and cast iron and ductile iron materials. Also suitable as base metals are magnesium, copper, nickel, titanium and alloys thereof.
The reinforcing filler addition particl~s are very fine and average from 1-100 micron in size. The particles can be metals which do not form chemical compounds with the matrix elements, such as Si in Al; intermetallics such as: TiA13 ZrA13 FeA13, Fe2Al5, CrA17, CrA13, NiA13, Co2A19, ScA13; carbides such as:5iC, TiC, WC, :,. ':;
,~ .
2~605 NbC, Fe3C; nitrides such as TiN, Si3N4, ZrN; borides such as TiB2, AlB2; oxides such as: ZrO2, Al203, Tio2,B2o3; and also other ceramic materials such as sapphire, glasses, graphite and carbo-nitrides.
Other particle materials used in the dispersion strengthening of metals can be used, provided they satisfactorily retain thermodynamic stability throughout the steps of the present process.
The entraining inert gases used in the present invention are preferably argon or helium although other inert gases are usable.
The inert gas is ionized and the entrained particles are preheated in the ionized gas prior to being injected into the melt to a high temperature below that at which the particles melt or sublime or dissociate; i.e. about O.9 of the melting point, sublimation temperature, or dissociation temperature as the case may be. At a higher temperature, the particles either agglomerate to produce undesirably large particles in the melt, or result in particles of a composition other than that, intended, or there occurs substantial depletion of the desired amount of particles in the melt. At particle temperatures below about O.S of the melting point (sublimation temperature or dissociation temperature) the resulting composite product does not exhibit the increase in strength, hardness and structural uniformity, uniformity of dispersed particles and homogeneity.
The temperature interval for particle preheating was determined experimentally based on the requirement of providing a necessary and sufficient degree of activation for interphase action 2~16~
ensuring a strong bond between the particles and base metal by removal of adsorbed oxygen from the surface of the particles in the course of ion etching and breaking by the particles in the base stream of the molten metal surface.
Determination of the appropriate temperature range applicable to a particular particle material can be determined from published temperature data in hand books or the like and the use of pyrometry devices such as from Agema with precision of + 1C. However, it is frequently more convenient, particularly when particles such as intermetallics or others are involved and the published data is not conveniently available, to establish base-line conditions. For example, prior to the making of composites, a test run is performed with the gas ionization apparatus to be used for the preheating step, for a particular particle loading and the gas flow and the residence time of the particles in the ionized gas is increased to that just required to melt (volatilize or dissociate) the particle is observed and then slightly reduced to avoid melting, etc. These process conditions then represent the 0.9 melting point temperature. A residence time of about 1/2 the residence time at which particle melting occurs will correspond to 0.5 melting point.
The empirical intervals can similarly be determined by adjusting gas flow and particle loading of the gas following fundamental concepts well known to the art.
A selection of particularly effective particle materials for use in the present invention is listed in Table A hereinbelow with temperature ranges and suitable, exemplary base metal compositions ,. ..
,. . -,: : , . , :~ . :
~ . . .
.
:: , : ~ ` : .
. , ~: . , , - 2~al~
also indicated.
TAsL~ A
Additive Particle Particle Temperature Base (Composition) Size Range C Melt micron ___________________________________________________________________ SiC 5-50 1100 - 2000 Al, Al alloys, Al-4%Cu-1.5% Mg - 0 5%Mn, Ti Al3 1-10 670 - 1200 Al, Al alloys, Al-4%Cu-1.5~ Mg ___________________________________________________________________ Ti B2 5-10 1400-2500 Al,Al base alloys Si3N4 1-5 950-1710 Cu,Ni Graphite 5-50 1800-3240 A1-12% Si ______________~___________________________________________________ In the present invention, from about 0.5% by weight up to about 25~ by weight of filler material can be incorporated in a base metal bath of molten metal and the particular material and amount added is determined on the basis of concepts known in the art to achieve a particular enhancement or combination of mechanical properties, e.g. hardness, strength, ductility, elasticity.
2~60~
Table B hereinbelow shows exemplary particle contents and base materials and an indication of the enhanced mechanical properties TABLE B
____________________________________________________ ______________ Particle Quantity Base Metal Enhanced (Composition) Wt. % (Composition) Property __________________________________________________________________ 1. SiC lQ Al Rm=200MPa,E=120 XN
MM2, ~~z 2. ZrA13 +Cr Al3 1 + 1 Al ~-2 = 99 Rm TiAl3 15 Al S1 = 300 Where: Rm - temporary tensile strength ~ proof stress E - Modulus of Elasticity K - rate of linear wear S - specific density of particles in the matrix 1,2,3 - indices applicable to aluminum base composite material, aluminum and A1-10% Ti 5 ~ ~
In the practice of the present invention, it is important that the molten base metal be physically agitated e.g. by being subjected to a stirring force continuously from the commencement of the introduction of solid particles until casting and solidification of the cast metal is complete. Initially, the base melt is in physical agitation, i.e. in a crucible type vessel and a stirring force is suitably and preferably applied to the base metal bath by non-interfering contact magnetic means as know to the art. At this stage of the process mechanical stirring using impellers of known type can also be used. The degree of stirring should vigorous enough e.g. a continuous observable rolling of the bath, to ensure uniform dispersion of the additive particles and test samples can be taken at intervals to so determine. When the particle containing base metal melt is ready for casting the material is transferred directly to a suitable mold and physical agitation is maintained in the molten material in the mold, suitably by vibration, e.g. ultrasound energy coupled to the outside of the mold and causing vibrations in the molten metal until all of the metal in the mold has solidified. The application of ultrasound to provide physical agitation should be of sufficient strength to maintain the uniformity achieved in the crucible but should not result in any significant visible motion of the mass of the molten metal.
In the practice of the present invention the stream of ionized inert gas with entrained solid particles is injected into the base metal bath so that the solid particles enter the bath to a depth of ,, ~a~l6~
at least 5 cm, e.g. about 10~ of the bath depth.
Continuous stirring in the course of change of the volume of the liquid phase from 100% to 0%, i.e. complete solidification, is a prerequisite of the present invention for ensuring uniform distribution of reinforcing material in the volume of the matrix enabled by the previous steps of the process and enhancement of wetability at the "particle-melt" interface. Lack of stirring at any stage of liquid-solid state of the composite material can result in weakening the surface contact between the base metal matrix and particles, and the undesirable formation of la~inations, segregations and non-uniformities of chemical and structural composition.
The thermodynamic stability of particles in the matrix melt inhibits their chemical action with the base metal and the formation of undesirable compounds of uncontrolled sizes and shapes, thus ensuring, in contrast to the prior art technology, the formation of superfine particle-reinforced alloys by melting the base metal, followed by combined crystallization and heat treatment, and the production of composite materials of "metal-intermetallide ~metal)" type with preset values of quantity, sizes and shapes of reinforcing phases.
With reference to Figure 1, a crucible (10) suitably made of graphite contains a molten metal bath (1) of matrix metal e.g.
aluminum which is stirred by way of a conventional magnetic inductor 4 to physically agitate the metal bath (1), preferably in the vigorous rotating motion shown in Figure 1. The crucible (10) 205~05 is provided with a protective cover (15) in which is installed an ionization chamber (2) of extended length. Ihert gas, e.g. argon is controllably introduced from lines (8) into ionization chamber (2) and the gas is ionized to produce a plasma arc in accordance with known techniques, and very high temperatures are developed in the ionization chamber (2) ranging from 8000 deg. C to 20000 deg.C.
Finely divided filler material is held in hopper (3) with metering means (not shown) for measuring the weight of finely divided filler material which is introduced via conduit (16) into the ionization chamber (2). The filler particles entering ionization chamber (2) are rapidly heated to a high temperature below that at which melting of the particles occurs, e.g. between 0.5 and 0.9 of the melting point temperature of the particles. The thus heated and activated particles entrained in a stream of the ionized inert gas (25) are introduced into the molten bath (1) by injection of the inert gas and penetration thereof below the surface of the metal bath. The continuous physical agitation of the metal bath (1) by magnetic inductor 4 establishes a uniform dispersion of the solid heated activated filler particles. The temperature of the metal bath is measured, e.g. by thermocouples (not shown) to ensure that the temperature is below that at which undesirable melting or decomposition of the filler particles occurs. Uniformity of dispersion of the filler particles in the bath is established by analyzing samples taken from bath at convenient intervals. When the pre-determined desired amount of solid filler particles have been introduced into the molten metal bath, plug ~5) at the base of .
~0~160~
crucible (lO) is opened and molten metal containing the solid additive particles (o) is introduced into mold (6) e.g. suitably made of steel. The molten metal is caused to solidify in the mold and surrounds the uniformly dispersed solid filler particles. To ensure that the solid filler particles remain uniformly dispersed in the molten metal phase as solidification progresses, an ultrasound transducer (7) is coupled to mold (5) so that molten metal in the mold is physically agitated by ultrasonic energy vibrations until all of the molten phase has passed into the solid state.
Figure 4(A) shows the crucible of Figure 1 provided with a conduit (20) for introducing reactant into ionization chamber (2') with an increased velocity of the ionized gas being indicated at (25) resulting in deeper penetration of the additive into the metal bath. Figure 4(B) shows the crucible of Figure 4(A) with ionized gas and additive being introduced at the bottom of the ladle. The inert gas forms bubbles (30) which are broken up and dispersed by ultrasonic transducer (12) in contact with the upper portion of the metal bath at its surface.
Figure 5 shows the crucible of Figure 4(B) with the ultrasonic transducer (12) and the injection of ionized gas (25) being offset ~rom the central alignment of Figure 4(B) to achieve the illustrated upwardly spiralling movement of the particle containing bubbles (30).
-, . '',. .
, - ,. . ''.~,,,' ' . , ~
20~60~
EXAMPLE
For testing the method of the invention use was made of unalloyed metals-aluminum and iron, as well as an aluminum base alloy 4~Cu, 1.5% Mg, 0.5% Mn~ ~ ese materia~s were separately used as the base melt for production of various composite materials.
The starting reinforcing materials used were powdered silicon carbide, 5 - 50 micron in size, titanium aluminide TiAl3 with particle size of 1-10 micron, and also titanium powder 10-loo micron in size.
Tests to produce composite materials were run in the pilot unit, shown schematically in Fig. 1. The crucible was made of graphite and contained a matrix melt (1) which was injected with a stream of ionized argon gas with entrained reinforcing particles preheated to predetermined temperature by means of a conventional plasmatron type ionization device (2) fitted with the metering device (3) to establish a predetermined rate of powder flow through the ionization device. The temperature of the particles, Tp was varied and was monitored by detecting the change in neat content of the base melt before and after injection of particles of powder.
Tp was calculated by the formula:
Tp= 6 m m (¦-- TDJ ( l + KN ) ) ' ~ , - 20~160~
where: ~ - melt temperature after inject of additives, C;
T~ - matrix temperature before injection of additives, C;.
C~ - specific heat of matrix metal, M~ - metal mass, K9 Cp - specific heat of particles, Mp - particles' mas, Kg Kn ~ dimensionless factor taking into account heat effects upon air cooling of melt surface during preheating in treatment by stream of ionized gas without injection of particles, Kn = 0.05-0.06 for 5 Kg of molten metal and an metal and an ionized argon gas flow of 0.1 M3/min.
Stirring the mix in the course of injection of additives casting was accomplished by means of the magnetic inductor (4).
After injection of predetermined quantities of solid additives the plug (5) was removed from the crucible and a liquids-solid mixture ~lowed through the hole in the crucible bottom to fill a casting mold made of steel. The steel mold (6), 50 mm diameter, was used and the molten metal-solid particle mix was stirred by ultrasound generator (7) until the mold contents solidified. The resulting solid casting of 2.5 kg. was hot extruded. Quality assessment of resulting composite material was determining the following parameters:
-chemical and structural uniformity, -size of reinforcing particles, -strength of composite material.
. . . .
. , : . . . . , ~, ,, , . ;- , 2~5:~0~
Chemical non-unifcrmity of composite material was evaluated by change in content of components of reinforcing particles in various cross-sections of the casting across the casting direction by determining the chemical non-uniformity factor K:
C ~ Cn~
C I ~ C
Where: Ck - content of components of reinforcing particles in cross-section of the casting, wt. ~;
n - number of cross sections analyzed;
Cmax Cmjn - maximum and minimum content of components of reinforcing particles in cross-sections, wt. %.
Structural non-uniformity of the composite material was assessed by change of average sizes of reinforcing particles by the factr Kave the factor KaVe:
d ~i~
n ~1 Where d~ - average size of i-th particle, micron;
dmaX dmjn - maximum and minimum sizes of analyzed particles n - number of analyzed particles. O
Strength was assessed by measuring the ultimate tensile strength Rml MPa (UTS). Chemical composition was determined by the quantimeter ARL 72000, with a precision of + 0.01%; structural characteristics were determined by the metallographic optic ~0~160~
microscope MeF-3A at magnifications up to 3000X and the structural analyzer Omnimet 2 for quantitative determination of elements in the structure. Determination of strength was by the tensile machine UTS-100 with maximum applied force of 100 KN. All of the foregoing equipment is state-of-the-art. Table 1 shows the results of the tests.
The resulting data proves that the best characteristics are ensured by the samples of composite materials produced in the experiments No. 6, 9, 12, 36, 42, 51, 57, 66, 69, 72 in accordance with the method of the present invention for production of metal base composite materials.
In a further embodiment of the present invention, filler material for the making of a composite material is synthesized in the environment of an ionized entraining gas and the thus produced nascent materials, shielded by the cleaning ionized gas, are introduced into the base metal melt which is physically agitated, e.g. by magnetic and ultrasound techniques to uniformly distribute the synthesized material in the base metal matrix. The filler materials are synthesized by introducing substantially stoichiometric amounts of the reactants for producing the filler material. For example, in making titanium nitride filler material titanium powder suitable sized 20-50 micron is entrained in nitrogen gas in proportions corresponding to the equation:
2 Ti + N2 ----2 TiN
The titanium/nitrogen mixture is passed into a stream of ionized inert gas and exposed to the ionized gas at a temperature -~ , ; ;:
: .
. - ~ , -20~60~
in the range of 2200-3000 degrees C for a time sufficient to complete reaction between the titanium and nitrogen to form titanium nitride in vapor form which is carried by the ionized inert gas onto the surface of the base metal melt, e.g. aluminum, which is physically agitated to unlformly disperse the titanium nitride in small discrete volumes which, on solidification in the base metal, provide ultrafine strengthening filler particles.
Other filler materials can be similarly synthesized as follows:
3Si (powder) +2N2----Si3N4 Ti (powder) + 3Al (powder)----TiAl3 The temperature of the base metal melt is maintained at a temperature which will quench the additive materials so that the synthesized additive material is not undesirably dissolved in the melt.
In another embodiment of the invention, a carbon bearing gas, such as the hydrocarbons, propane, butane natural gas, methane, or carbon monoxide, carbon dioxide are ionized in mixture with a stream of ionized inert gas and dissociated. The carbon dissociation product is monatomic elemental carban which is in~ected into the base melt as a filler addition. For the oxygen bearing gases, the liberated monatomic oxygen is an ionized gas stream which reacts with the melt, e.g. aluminum, to form ultrafine filler particles of aluminum oxide, Al2O3 in the melt.
Following the practice of the present invention under the condition of Table 2 and using the materials of Table 2, the ~:
20al~0a indicated additives were introduced into the indicated molten base metal matrix to produce composite materials having improved mechanical properties.
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SUM~ARY OF THE INVENTION
An object of the present invention is improvement in quality of composite materials by increasinq the uniformity of dispersion of reinforcing filler particles and the strength of their adhesion with the base metal matrix and the ability to provide an expanded group of composite materials by the use of a wide range of ceramic particles, metals and intermetallics including carbides, nitrides, borides, oxides, graphite and glasses.
The foregoing object and other objects are achieved by a method o~ making composite materials which includes the steps of entraining finely divided solid additive particles, e.g. of a ceramic, metal, lntermetallic including oxides, borides, carbides, nitrides, graphite, glasses in an inert gas and ionizing the entraining inert gas t~ heat the solid particles to a high temperature which is less than the temperature at which the particles become non-solid due to melting, sublimation, or dissociation, but more than about 1/2 of such temperature, and 2~5160~
injecting a stream of the ionized entraining gas and entrained heated solid particles into a molten metal mass while maintaining a stirring movement in the mass of molten metal sufficient to promote and to maintain dispersion of the added particles to solidify in a composite mass while maintaining a stirring movement in the solid particle-containing molten metal until solidification thereof is complete.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1, 4 and 5 show apparatus for the practice of various embodiments of the invention: and Figures 2 and 3 are representations of metallurgical conditions which occur in the course of alloy formation.
DETAlLED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the practice of the present invention, the base metal melt can be aluminum, iron, copper, magnesium, nickel, cobalt, chromium.
Suitable base metals are alloys of the above-mentioned metals in which they are the predominant constituent, such as aluminum containing up to 40~ by weight manganese, and steels, and cast iron and ductile iron materials. Also suitable as base metals are magnesium, copper, nickel, titanium and alloys thereof.
The reinforcing filler addition particl~s are very fine and average from 1-100 micron in size. The particles can be metals which do not form chemical compounds with the matrix elements, such as Si in Al; intermetallics such as: TiA13 ZrA13 FeA13, Fe2Al5, CrA17, CrA13, NiA13, Co2A19, ScA13; carbides such as:5iC, TiC, WC, :,. ':;
,~ .
2~605 NbC, Fe3C; nitrides such as TiN, Si3N4, ZrN; borides such as TiB2, AlB2; oxides such as: ZrO2, Al203, Tio2,B2o3; and also other ceramic materials such as sapphire, glasses, graphite and carbo-nitrides.
Other particle materials used in the dispersion strengthening of metals can be used, provided they satisfactorily retain thermodynamic stability throughout the steps of the present process.
The entraining inert gases used in the present invention are preferably argon or helium although other inert gases are usable.
The inert gas is ionized and the entrained particles are preheated in the ionized gas prior to being injected into the melt to a high temperature below that at which the particles melt or sublime or dissociate; i.e. about O.9 of the melting point, sublimation temperature, or dissociation temperature as the case may be. At a higher temperature, the particles either agglomerate to produce undesirably large particles in the melt, or result in particles of a composition other than that, intended, or there occurs substantial depletion of the desired amount of particles in the melt. At particle temperatures below about O.S of the melting point (sublimation temperature or dissociation temperature) the resulting composite product does not exhibit the increase in strength, hardness and structural uniformity, uniformity of dispersed particles and homogeneity.
The temperature interval for particle preheating was determined experimentally based on the requirement of providing a necessary and sufficient degree of activation for interphase action 2~16~
ensuring a strong bond between the particles and base metal by removal of adsorbed oxygen from the surface of the particles in the course of ion etching and breaking by the particles in the base stream of the molten metal surface.
Determination of the appropriate temperature range applicable to a particular particle material can be determined from published temperature data in hand books or the like and the use of pyrometry devices such as from Agema with precision of + 1C. However, it is frequently more convenient, particularly when particles such as intermetallics or others are involved and the published data is not conveniently available, to establish base-line conditions. For example, prior to the making of composites, a test run is performed with the gas ionization apparatus to be used for the preheating step, for a particular particle loading and the gas flow and the residence time of the particles in the ionized gas is increased to that just required to melt (volatilize or dissociate) the particle is observed and then slightly reduced to avoid melting, etc. These process conditions then represent the 0.9 melting point temperature. A residence time of about 1/2 the residence time at which particle melting occurs will correspond to 0.5 melting point.
The empirical intervals can similarly be determined by adjusting gas flow and particle loading of the gas following fundamental concepts well known to the art.
A selection of particularly effective particle materials for use in the present invention is listed in Table A hereinbelow with temperature ranges and suitable, exemplary base metal compositions ,. ..
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TAsL~ A
Additive Particle Particle Temperature Base (Composition) Size Range C Melt micron ___________________________________________________________________ SiC 5-50 1100 - 2000 Al, Al alloys, Al-4%Cu-1.5% Mg - 0 5%Mn, Ti Al3 1-10 670 - 1200 Al, Al alloys, Al-4%Cu-1.5~ Mg ___________________________________________________________________ Ti B2 5-10 1400-2500 Al,Al base alloys Si3N4 1-5 950-1710 Cu,Ni Graphite 5-50 1800-3240 A1-12% Si ______________~___________________________________________________ In the present invention, from about 0.5% by weight up to about 25~ by weight of filler material can be incorporated in a base metal bath of molten metal and the particular material and amount added is determined on the basis of concepts known in the art to achieve a particular enhancement or combination of mechanical properties, e.g. hardness, strength, ductility, elasticity.
2~60~
Table B hereinbelow shows exemplary particle contents and base materials and an indication of the enhanced mechanical properties TABLE B
____________________________________________________ ______________ Particle Quantity Base Metal Enhanced (Composition) Wt. % (Composition) Property __________________________________________________________________ 1. SiC lQ Al Rm=200MPa,E=120 XN
MM2, ~~z 2. ZrA13 +Cr Al3 1 + 1 Al ~-2 = 99 Rm TiAl3 15 Al S1 = 300 Where: Rm - temporary tensile strength ~ proof stress E - Modulus of Elasticity K - rate of linear wear S - specific density of particles in the matrix 1,2,3 - indices applicable to aluminum base composite material, aluminum and A1-10% Ti 5 ~ ~
In the practice of the present invention, it is important that the molten base metal be physically agitated e.g. by being subjected to a stirring force continuously from the commencement of the introduction of solid particles until casting and solidification of the cast metal is complete. Initially, the base melt is in physical agitation, i.e. in a crucible type vessel and a stirring force is suitably and preferably applied to the base metal bath by non-interfering contact magnetic means as know to the art. At this stage of the process mechanical stirring using impellers of known type can also be used. The degree of stirring should vigorous enough e.g. a continuous observable rolling of the bath, to ensure uniform dispersion of the additive particles and test samples can be taken at intervals to so determine. When the particle containing base metal melt is ready for casting the material is transferred directly to a suitable mold and physical agitation is maintained in the molten material in the mold, suitably by vibration, e.g. ultrasound energy coupled to the outside of the mold and causing vibrations in the molten metal until all of the metal in the mold has solidified. The application of ultrasound to provide physical agitation should be of sufficient strength to maintain the uniformity achieved in the crucible but should not result in any significant visible motion of the mass of the molten metal.
In the practice of the present invention the stream of ionized inert gas with entrained solid particles is injected into the base metal bath so that the solid particles enter the bath to a depth of ,, ~a~l6~
at least 5 cm, e.g. about 10~ of the bath depth.
Continuous stirring in the course of change of the volume of the liquid phase from 100% to 0%, i.e. complete solidification, is a prerequisite of the present invention for ensuring uniform distribution of reinforcing material in the volume of the matrix enabled by the previous steps of the process and enhancement of wetability at the "particle-melt" interface. Lack of stirring at any stage of liquid-solid state of the composite material can result in weakening the surface contact between the base metal matrix and particles, and the undesirable formation of la~inations, segregations and non-uniformities of chemical and structural composition.
The thermodynamic stability of particles in the matrix melt inhibits their chemical action with the base metal and the formation of undesirable compounds of uncontrolled sizes and shapes, thus ensuring, in contrast to the prior art technology, the formation of superfine particle-reinforced alloys by melting the base metal, followed by combined crystallization and heat treatment, and the production of composite materials of "metal-intermetallide ~metal)" type with preset values of quantity, sizes and shapes of reinforcing phases.
With reference to Figure 1, a crucible (10) suitably made of graphite contains a molten metal bath (1) of matrix metal e.g.
aluminum which is stirred by way of a conventional magnetic inductor 4 to physically agitate the metal bath (1), preferably in the vigorous rotating motion shown in Figure 1. The crucible (10) 205~05 is provided with a protective cover (15) in which is installed an ionization chamber (2) of extended length. Ihert gas, e.g. argon is controllably introduced from lines (8) into ionization chamber (2) and the gas is ionized to produce a plasma arc in accordance with known techniques, and very high temperatures are developed in the ionization chamber (2) ranging from 8000 deg. C to 20000 deg.C.
Finely divided filler material is held in hopper (3) with metering means (not shown) for measuring the weight of finely divided filler material which is introduced via conduit (16) into the ionization chamber (2). The filler particles entering ionization chamber (2) are rapidly heated to a high temperature below that at which melting of the particles occurs, e.g. between 0.5 and 0.9 of the melting point temperature of the particles. The thus heated and activated particles entrained in a stream of the ionized inert gas (25) are introduced into the molten bath (1) by injection of the inert gas and penetration thereof below the surface of the metal bath. The continuous physical agitation of the metal bath (1) by magnetic inductor 4 establishes a uniform dispersion of the solid heated activated filler particles. The temperature of the metal bath is measured, e.g. by thermocouples (not shown) to ensure that the temperature is below that at which undesirable melting or decomposition of the filler particles occurs. Uniformity of dispersion of the filler particles in the bath is established by analyzing samples taken from bath at convenient intervals. When the pre-determined desired amount of solid filler particles have been introduced into the molten metal bath, plug ~5) at the base of .
~0~160~
crucible (lO) is opened and molten metal containing the solid additive particles (o) is introduced into mold (6) e.g. suitably made of steel. The molten metal is caused to solidify in the mold and surrounds the uniformly dispersed solid filler particles. To ensure that the solid filler particles remain uniformly dispersed in the molten metal phase as solidification progresses, an ultrasound transducer (7) is coupled to mold (5) so that molten metal in the mold is physically agitated by ultrasonic energy vibrations until all of the molten phase has passed into the solid state.
Figure 4(A) shows the crucible of Figure 1 provided with a conduit (20) for introducing reactant into ionization chamber (2') with an increased velocity of the ionized gas being indicated at (25) resulting in deeper penetration of the additive into the metal bath. Figure 4(B) shows the crucible of Figure 4(A) with ionized gas and additive being introduced at the bottom of the ladle. The inert gas forms bubbles (30) which are broken up and dispersed by ultrasonic transducer (12) in contact with the upper portion of the metal bath at its surface.
Figure 5 shows the crucible of Figure 4(B) with the ultrasonic transducer (12) and the injection of ionized gas (25) being offset ~rom the central alignment of Figure 4(B) to achieve the illustrated upwardly spiralling movement of the particle containing bubbles (30).
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20~60~
EXAMPLE
For testing the method of the invention use was made of unalloyed metals-aluminum and iron, as well as an aluminum base alloy 4~Cu, 1.5% Mg, 0.5% Mn~ ~ ese materia~s were separately used as the base melt for production of various composite materials.
The starting reinforcing materials used were powdered silicon carbide, 5 - 50 micron in size, titanium aluminide TiAl3 with particle size of 1-10 micron, and also titanium powder 10-loo micron in size.
Tests to produce composite materials were run in the pilot unit, shown schematically in Fig. 1. The crucible was made of graphite and contained a matrix melt (1) which was injected with a stream of ionized argon gas with entrained reinforcing particles preheated to predetermined temperature by means of a conventional plasmatron type ionization device (2) fitted with the metering device (3) to establish a predetermined rate of powder flow through the ionization device. The temperature of the particles, Tp was varied and was monitored by detecting the change in neat content of the base melt before and after injection of particles of powder.
Tp was calculated by the formula:
Tp= 6 m m (¦-- TDJ ( l + KN ) ) ' ~ , - 20~160~
where: ~ - melt temperature after inject of additives, C;
T~ - matrix temperature before injection of additives, C;.
C~ - specific heat of matrix metal, M~ - metal mass, K9 Cp - specific heat of particles, Mp - particles' mas, Kg Kn ~ dimensionless factor taking into account heat effects upon air cooling of melt surface during preheating in treatment by stream of ionized gas without injection of particles, Kn = 0.05-0.06 for 5 Kg of molten metal and an metal and an ionized argon gas flow of 0.1 M3/min.
Stirring the mix in the course of injection of additives casting was accomplished by means of the magnetic inductor (4).
After injection of predetermined quantities of solid additives the plug (5) was removed from the crucible and a liquids-solid mixture ~lowed through the hole in the crucible bottom to fill a casting mold made of steel. The steel mold (6), 50 mm diameter, was used and the molten metal-solid particle mix was stirred by ultrasound generator (7) until the mold contents solidified. The resulting solid casting of 2.5 kg. was hot extruded. Quality assessment of resulting composite material was determining the following parameters:
-chemical and structural uniformity, -size of reinforcing particles, -strength of composite material.
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Chemical non-unifcrmity of composite material was evaluated by change in content of components of reinforcing particles in various cross-sections of the casting across the casting direction by determining the chemical non-uniformity factor K:
C ~ Cn~
C I ~ C
Where: Ck - content of components of reinforcing particles in cross-section of the casting, wt. ~;
n - number of cross sections analyzed;
Cmax Cmjn - maximum and minimum content of components of reinforcing particles in cross-sections, wt. %.
Structural non-uniformity of the composite material was assessed by change of average sizes of reinforcing particles by the factr Kave the factor KaVe:
d ~i~
n ~1 Where d~ - average size of i-th particle, micron;
dmaX dmjn - maximum and minimum sizes of analyzed particles n - number of analyzed particles. O
Strength was assessed by measuring the ultimate tensile strength Rml MPa (UTS). Chemical composition was determined by the quantimeter ARL 72000, with a precision of + 0.01%; structural characteristics were determined by the metallographic optic ~0~160~
microscope MeF-3A at magnifications up to 3000X and the structural analyzer Omnimet 2 for quantitative determination of elements in the structure. Determination of strength was by the tensile machine UTS-100 with maximum applied force of 100 KN. All of the foregoing equipment is state-of-the-art. Table 1 shows the results of the tests.
The resulting data proves that the best characteristics are ensured by the samples of composite materials produced in the experiments No. 6, 9, 12, 36, 42, 51, 57, 66, 69, 72 in accordance with the method of the present invention for production of metal base composite materials.
In a further embodiment of the present invention, filler material for the making of a composite material is synthesized in the environment of an ionized entraining gas and the thus produced nascent materials, shielded by the cleaning ionized gas, are introduced into the base metal melt which is physically agitated, e.g. by magnetic and ultrasound techniques to uniformly distribute the synthesized material in the base metal matrix. The filler materials are synthesized by introducing substantially stoichiometric amounts of the reactants for producing the filler material. For example, in making titanium nitride filler material titanium powder suitable sized 20-50 micron is entrained in nitrogen gas in proportions corresponding to the equation:
2 Ti + N2 ----2 TiN
The titanium/nitrogen mixture is passed into a stream of ionized inert gas and exposed to the ionized gas at a temperature -~ , ; ;:
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in the range of 2200-3000 degrees C for a time sufficient to complete reaction between the titanium and nitrogen to form titanium nitride in vapor form which is carried by the ionized inert gas onto the surface of the base metal melt, e.g. aluminum, which is physically agitated to unlformly disperse the titanium nitride in small discrete volumes which, on solidification in the base metal, provide ultrafine strengthening filler particles.
Other filler materials can be similarly synthesized as follows:
3Si (powder) +2N2----Si3N4 Ti (powder) + 3Al (powder)----TiAl3 The temperature of the base metal melt is maintained at a temperature which will quench the additive materials so that the synthesized additive material is not undesirably dissolved in the melt.
In another embodiment of the invention, a carbon bearing gas, such as the hydrocarbons, propane, butane natural gas, methane, or carbon monoxide, carbon dioxide are ionized in mixture with a stream of ionized inert gas and dissociated. The carbon dissociation product is monatomic elemental carban which is in~ected into the base melt as a filler addition. For the oxygen bearing gases, the liberated monatomic oxygen is an ionized gas stream which reacts with the melt, e.g. aluminum, to form ultrafine filler particles of aluminum oxide, Al2O3 in the melt.
Following the practice of the present invention under the condition of Table 2 and using the materials of Table 2, the ~:
20al~0a indicated additives were introduced into the indicated molten base metal matrix to produce composite materials having improved mechanical properties.
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Claims (13)
1. Method of making a composite material comprising entraining finely divided solid additive particles, in a stream of ionized inert gas and ionizing the inert gas and utilizing heat generated by the ionized gas to heat the solid particles to a high temperature which is less than the temperature in at which the solid particles become non-solid due to melting, sublimination or dissociation, but more than about 1/2 of such temperature of melting, sublimation or dissociation, and injecting said stream of gas and entrained heated solid particles into a molten metal mass to provide a mixture of finely divided solid particles and molten metal and thereafter causing physical agitation of the mixture of molten metal and solid particles to establish a substantially uniform distribution of solid particles in the molten metal and continuing physical agitation of molten metal until the mixture of finely divided particles and metal is completely solidified.
2. Method in accordance with claim 1 wherein the mixture of molten metal and solid particles is initially contained in a crucible and agitation is provided by magnetic means external to the crucible and subsequently a portion of said mixture is transferred to a mold and agitation of the mixture is provided by ultrasound means external to the mold.
3. Method for making a composite material comprising entraining in a stream of ionized inert gas finely divided solid and/or gaseous reactant in proportions to provide upon reaction a predetermined composition, causing reaction between said reactants while entrained in said ionized inert gas to provide a reaction product to penetrate into a molten metal bath, and causing physical agitation of said metal bath to uniformly disperse said reaction product therein.
4. Method in accordance with Claim 1 wherein said base metal is selected from aluminum, iron, magnesium, copper, nickel, chromium, titanium and said additive material is selected from two-or multi- component chemical compounds of one of the base metals with other metals as well as from carbides, nitrides, carbonitrides, oxides and borides of metals.
5. A composite material or alloy with uniformly distributed components formed by injecting additive particles which have been heated by an ionized gas into a physically agitated molten base metal, the resulting material being continuously removed from the zone of injection, with subsequent cooling while physical agitation is continuously maintained.
6. Composite material or alloy in accordance with Claim 5 wherein said base metal is selected from aluminum, iron, magnesium, copper, nickel, chromium, titanium and said additive material is selected from two- or multi- component compounds of the base metals with other metals as well as from carbides, nitrides, carbonitrides, oxides and borides of metals.
7. Apparatus for making a composite material comprising:
(i) crucible means for containing a molten base metal;
(ii) plasma generating means positioned adjacent the crucible means for receiving a stream of inert gas and entrained filler particles and ionizing said gas and thereby heating said particles;
(iii) means for injecting said ionized gas and heated particles into said crucible means to penetrate into molten metal when present in said crucible;
(iv) means for continuously agitating molten metal when present in said crucible;
(v) mold means for receiving molten metal containing filler particles from said crucible; and (vi) means for continuously agitating molten metal when present in said mold means.
(i) crucible means for containing a molten base metal;
(ii) plasma generating means positioned adjacent the crucible means for receiving a stream of inert gas and entrained filler particles and ionizing said gas and thereby heating said particles;
(iii) means for injecting said ionized gas and heated particles into said crucible means to penetrate into molten metal when present in said crucible;
(iv) means for continuously agitating molten metal when present in said crucible;
(v) mold means for receiving molten metal containing filler particles from said crucible; and (vi) means for continuously agitating molten metal when present in said mold means.
8. Apparatus in accordance with Claim 7 wherein said crucible is covered and the means for injecting ionized gas and heated particles passes through said cover.
9. Apparatus in accordance with Claim 7 wherein the means for agitating molten metal in the crucible are magnetic stirring means.
10. Apparatus in accordance with Claim 7 wherein the means for agitating molten metal in the mold means is ultrasonic transducer means.
11. Apparatus in accordance with Claim 7 wherein the means for injecting ionized gas and heated particles passes through the bottom of said crucible.
12. Apparatus in accordance with Claim 11 wherein ultrasonic transducer means are provided adjacent the upper portion of the crucible means
13. Apparatus in accordance with Claim 12 wherein the ultrasonic transducer and means for injecting ionized gas and heated particles are horizontally displaced so that molten metal in the crucible is subjected to rotational movement.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU4867973/02A RU2020042C1 (en) | 1990-09-19 | 1990-09-19 | Method of manufacture of composite material castings on metal base |
SU4867973 | 1990-09-19 | ||
US07/740,823 | 1991-08-08 | ||
US07/740,823 US5305817A (en) | 1990-09-19 | 1991-08-08 | Method for production of metal base composite material |
Publications (1)
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CA2051605A1 true CA2051605A1 (en) | 1992-03-20 |
Family
ID=26666243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002051605A Abandoned CA2051605A1 (en) | 1990-09-19 | 1991-09-17 | Method and apparatus for production of metal base composite material |
Country Status (9)
Country | Link |
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JP (1) | JPH0673469A (en) |
CN (1) | CN1062769A (en) |
BR (1) | BR9103931A (en) |
CA (1) | CA2051605A1 (en) |
DE (1) | DE4131239C2 (en) |
ES (1) | ES2036134B1 (en) |
FR (1) | FR2666819B1 (en) |
GB (1) | GB2248071A (en) |
IT (1) | IT1258217B (en) |
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CN1037013C (en) * | 1994-10-25 | 1998-01-14 | 北京工业大学 | Forming method of Al2O3 base casting composite material self-formed from reaction |
DE10320393A1 (en) * | 2003-05-06 | 2004-11-25 | Hallberg Guss Gmbh | Production of tribological cast parts, especially engine blocks, made from iron alloys comprises adding hard stable particles to the melt shortly before, during or after casting to obtain embedded particles in the solidified structure |
JP4852737B2 (en) * | 2004-09-27 | 2012-01-11 | 国立大学法人 千葉大学 | Method for producing recycled Fe-Al composite material |
JP4810942B2 (en) | 2005-09-20 | 2011-11-09 | トヨタ自動車株式会社 | Automatic stop device for internal combustion engine |
DE102006002337A1 (en) * | 2006-01-18 | 2007-07-19 | Bayerische Motoren Werke Ag | Process to strengthen aluminum alloy or magnesium alloy by admixture of micro- or nano-particles to molten metal |
TWI458837B (en) * | 2008-10-24 | 2014-11-01 | Hon Hai Prec Ind Co Ltd | Method for making magnesium matrix composite material |
CN101733368B (en) * | 2008-11-26 | 2012-04-25 | 北京有色金属研究总院 | Method for preparing metal-based composite material |
CN102108450B (en) * | 2009-12-25 | 2012-08-29 | 清华大学 | Method for preparing magnesium-based composite material |
DE102010008202B4 (en) * | 2010-02-17 | 2015-12-31 | Daimler Ag | Manufacturing method for a friction ring made of a composite material |
CN101851717B (en) | 2010-06-14 | 2012-09-19 | 清华大学 | Shell and sound producing device applying same |
CN101851716B (en) * | 2010-06-14 | 2014-07-09 | 清华大学 | Magnesium base composite material and preparation method thereof, and application thereof in sounding device |
US8858697B2 (en) | 2011-10-28 | 2014-10-14 | General Electric Company | Mold compositions |
US9011205B2 (en) | 2012-02-15 | 2015-04-21 | General Electric Company | Titanium aluminide article with improved surface finish |
US8932518B2 (en) | 2012-02-29 | 2015-01-13 | General Electric Company | Mold and facecoat compositions |
US8906292B2 (en) | 2012-07-27 | 2014-12-09 | General Electric Company | Crucible and facecoat compositions |
US8708033B2 (en) | 2012-08-29 | 2014-04-29 | General Electric Company | Calcium titanate containing mold compositions and methods for casting titanium and titanium aluminide alloys |
US8992824B2 (en) | 2012-12-04 | 2015-03-31 | General Electric Company | Crucible and extrinsic facecoat compositions |
US9592548B2 (en) | 2013-01-29 | 2017-03-14 | General Electric Company | Calcium hexaluminate-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
US9511417B2 (en) | 2013-11-26 | 2016-12-06 | General Electric Company | Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
US9192983B2 (en) | 2013-11-26 | 2015-11-24 | General Electric Company | Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
US10391547B2 (en) | 2014-06-04 | 2019-08-27 | General Electric Company | Casting mold of grading with silicon carbide |
RU2607016C2 (en) * | 2014-07-01 | 2017-01-10 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Method of producing a cast composite material |
DE102014222001B4 (en) * | 2014-10-29 | 2023-06-29 | Bayerische Motoren Werke Aktiengesellschaft | casting process |
CN104388793B (en) * | 2014-11-14 | 2016-05-25 | 苏州蔻美新材料有限公司 | A kind of medical metal ceramic material and preparation method thereof |
CN105300125B (en) * | 2015-11-30 | 2018-02-02 | 银邦金属复合材料股份有限公司 | One kind stirring and feed mechanism |
CN111041288B (en) * | 2019-12-18 | 2021-10-12 | 江苏大学 | High-toughness anti-fatigue in-situ aluminum-based composite material and preparation method thereof |
CN112048623A (en) * | 2020-09-07 | 2020-12-08 | 孔霄 | Aluminum alloy smelting and purifying equipment |
EP4373999A1 (en) * | 2021-07-20 | 2024-05-29 | Proto Materials LLC | Systems and methods for fabricating crystals of metal compounds |
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GB811803A (en) * | 1956-07-30 | 1959-04-15 | British Oxygen Co Ltd | Treatment of molten metals and alloys |
GB823428A (en) * | 1956-11-16 | 1959-11-11 | British Oxygen Co Ltd | Treatment of ferrous metal |
GB894729A (en) * | 1959-11-10 | 1962-04-26 | British Oxygen Co Ltd | Treatment of ferrous metal |
US3286334A (en) * | 1965-07-16 | 1966-11-22 | Contemporary Res Inc | Production of dispersion hardened materials |
US3547622A (en) * | 1968-06-12 | 1970-12-15 | Pennwalt Corp | D.c. powered plasma arc method and apparatus for refining molten metal |
FR2038858A5 (en) * | 1969-03-31 | 1971-01-08 | Combustible Nucleaire | |
US3678988A (en) * | 1970-07-02 | 1972-07-25 | United Aircraft Corp | Incorporation of dispersoids in directionally solidified castings |
JPS5841939B2 (en) * | 1976-12-29 | 1983-09-16 | 大同特殊鋼株式会社 | Heating device and heating method |
US4473103A (en) * | 1982-01-29 | 1984-09-25 | International Telephone And Telegraph Corporation | Continuous production of metal alloy composites |
US4786467A (en) * | 1983-06-06 | 1988-11-22 | Dural Aluminum Composites Corp. | Process for preparation of composite materials containing nonmetallic particles in a metallic matrix, and composite materials made thereby |
WO1989007499A1 (en) * | 1988-02-09 | 1989-08-24 | The Broken Hill Proprietary Company Limited | Superheating and microalloying of molten metal by contact with a plasma arc |
NO165766C (en) * | 1988-06-30 | 1991-04-10 | Norsk Hydro As | PROCEDURE FOR CORE REFINING METALS. |
GB9008833D0 (en) * | 1990-04-19 | 1990-06-13 | Boc Group Plc | Heating |
-
1991
- 1991-09-11 FR FR9111201A patent/FR2666819B1/en not_active Expired - Fee Related
- 1991-09-12 BR BR919103931A patent/BR9103931A/en unknown
- 1991-09-13 IT ITMI912431A patent/IT1258217B/en active IP Right Grant
- 1991-09-14 ES ES9102050A patent/ES2036134B1/en not_active Expired - Lifetime
- 1991-09-16 GB GB9119770A patent/GB2248071A/en not_active Withdrawn
- 1991-09-17 CA CA002051605A patent/CA2051605A1/en not_active Abandoned
- 1991-09-18 CN CN91109009.6A patent/CN1062769A/en active Pending
- 1991-09-18 JP JP3267217A patent/JPH0673469A/en active Pending
- 1991-09-19 DE DE4131239A patent/DE4131239C2/en not_active Expired - Fee Related
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IT1258217B (en) | 1996-02-21 |
DE4131239C2 (en) | 1996-12-05 |
ITMI912431A1 (en) | 1993-03-13 |
GB2248071A (en) | 1992-03-25 |
FR2666819A1 (en) | 1992-03-20 |
JPH0673469A (en) | 1994-03-15 |
CN1062769A (en) | 1992-07-15 |
ES2036134A1 (en) | 1993-05-01 |
BR9103931A (en) | 1992-05-26 |
ES2036134B1 (en) | 1994-04-01 |
GB9119770D0 (en) | 1991-10-30 |
ITMI912431A0 (en) | 1991-09-13 |
FR2666819B1 (en) | 1994-09-23 |
DE4131239A1 (en) | 1992-03-26 |
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