US3924098A - Heating element, method and composition - Google Patents
Heating element, method and composition Download PDFInfo
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- US3924098A US3924098A US421073A US42107373A US3924098A US 3924098 A US3924098 A US 3924098A US 421073 A US421073 A US 421073A US 42107373 A US42107373 A US 42107373A US 3924098 A US3924098 A US 3924098A
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- percent
- tailings
- composition
- mud
- heating element
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- Expired - Lifetime
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 12
- 239000002245 particle Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 20
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 238000005188 flotation Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000002288 cocrystallisation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052611 pyroxene Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910000809 Alumel Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 241000244489 Navia Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229940105305 carbon monoxide Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001179 chromel Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000003621 hammer milling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000395 magnesium oxide 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
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
- H05B3/28—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material
- H05B3/283—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material the insulating material being an inorganic material, e.g. ceramic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49082—Resistor making
- Y10T29/49083—Heater type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49082—Resistor making
- Y10T29/49101—Applying terminal
Definitions
- ABSTRACT A heating element is cast extruded or formed from a composition comprising finely comminuted ferrous metal in a matrix essentially consisting of a base composition consisting essentially of tailings muds from lithium ore extraction comprising a major percentage of silicon lesser percentages of aluminum and calcium, and to which some alkali metals or lead may he added in order to ease working and depress the melting point.
- An electrically conductive composition of controlied resistance is prepared in which the ferrous particles contact each other so as to give the resultant clement resistivity of 10*" to 1,000 Ohm centimeters.
- the tailings mud is a by-product from ore extraction. which is particularly suitable for this purpose because of its fine state of comminution and its workability.
- An object of the invention is a superior composition for electrical heating, utilizing a waste material.
- Another object is a method for preparing said composition, and heating elements made therefrom.
- a low cost product, heatable by electrical resistance to temperatures suitable for radiant heating of human dwellings and other applications calling for moderate temperature is prepared by mixing a finely comminuted electrically conductive particulate substance with a flotation mud from an ore refining process said mud comprising silica-alumina-calcia type tailings after milling, roasting and extracting; and compacting the resultant product so as to secure the desired electrical resistance for resistance heating, and stabilizing it, for example, by one or more of the following operations: further drying, compacting, sintering, or fusion and enameling steps.
- FIG. 1, FIG. 2, and FIG. are enlarged cross-sectional views.
- FIG. 3 and FIG. 4 are cross-sectional views.
- FIG. 6 is a perspective view.
- FIG. 1 illustrates a magnified (about X) section through a dispersion of conductive ore or metal fragments or particles in a matrix of fused flotation mud taken from the continuous vacuum (Oliver") filters, removing flotation mud from a process resulting in flotation tailings being formed following ore treating steps including milling, roasting, extracting and flotation.
- Oliver continuous vacuum
- This composite is referred to in the drawings as l0.
- the essential points are that the tailings used as raw material be finely comminuted, roasted, to remove volatiles and converted, as much as possible based on the raw material, to an oxide form suitable for glass formation. Subsequent leaching has removed the wateror acid-solubles. After the final flotation process, vacuum filtration removes the major percentage of water, thus leaving a pasty product in a form easily and economically handled and excellently suitable for blending with iron filings, crushed conductive metal ores, or oxides of ferrous or other ores reducible to conductive metal by treatment with reducing agents of which hydrogen, car bon monoxide, and hydrocarbon gases are the most convenient and inexpensive.
- the blending can be done on conventional blending equipment, such as, for example, continuous ribbon mixers such as Day double spiral ribbon mixers, or in sigma blade mixers, but most economically by multiple pass through differential speed rollers on a paint mill.
- conventional blending equipment such as, for example, continuous ribbon mixers such as Day double spiral ribbon mixers, or in sigma blade mixers, but most economically by multiple pass through differential speed rollers on a paint mill.
- FIG. 3 shows an embodiment in which the matrix is very thick, for example, like a brick or a concrete block 5, or other conventional building elements and the particles have been introduced only in a layer of about a couple mils to 36 inch, so that the building elements can be assembled and then heated by electric current conducted only through the thin layer.
- the particles can be introduced, for example, by projecting them into the still soft mass at high velocity by spraying or centrifugal throwing, with optional subsequent application of an enamel, or a sealing coat, for example, of soluble silica or silicate solution such as sodium silicate, or colloidal silicic acid solutions.
- FIG. 4 shows such a building element in which the main body is free from metal and has been foamed, for example, by inclusion of a gas forming sulfide or carbonate in the mix as well known in the art. 4 indicates bubbles, l0 the metal carrying conductive layer.
- FIG. 5 is a magnified detail view, showing a surface sealing layer 6 of enamel, silicate, or the like, to close such cracks as might form and enhance the resistance of the element to oxidation. It may also serve decorative purposes.
- FIG. 6 shows a perspective view of a heating element in panel form.
- 7 is the heating surface, 8 the electrodes attached thereto in any of the many manners known to the art.
- the electrode surface is applied before any sealant coat.
- the electrodes may be simply clamped firmly over the surface, or the surface may be first specially prepared by abrading and fusing over it a solder with appropriate flux to better bind the electrode. Since the art in this field is voluminous and throughly known, I believe further discussion of this aspect to be superfluous.
- EXAMPLE 1 A heating rod was made from the tailings mud from spodumene, a lithium aluminum silicate mineral, LiAl(SiO belonging to the pyroxene group, from which the lithium had been extracted by the steps of crushing, ballmilling 4 hours, roasting in a rotary kiln. cooling, extracting with dilute sulfuric acid. washing, froth flotation, and separation of the finely divided (over 50 percent through 325 mesh screen) wet mud on a rotary vacuum filter (Oliver filter).
- the tailings mud used in this experiment was a composite of four samples, and had the following analysis:
- This tailings mud was dried. and the resulting powder was mixed with volume percent of iron filings.
- the mixed powders were ballmilled together over night, and 17.5 grams were placed in a graphite mold 6 inches long by 56 inch wide and as inch deep of U-shaped cross section. The mold and powders were placed in a vacuum furnace, the pressure was reduced to below 10 Torricelli and the temperature raised.
- a half inch of each end of one 3 inch length of the above was painted with conductive silver paint, the remainder with Na siO solution and the coatings dried. Electrodes were attached to the silvered ends and the bar was subjected to several cycles of electrical heating to temperatures between 100 and 140 C.
- Temperatures were measured with thermally insulated chromel alumel thermocouples made of fine wires (0.005 inch dia.) electrically insulated from the heater bar by l/32 inch thick piece of boron nitride and recorded on a chart recorder. Current through. and potential across the bar were measured to an accuracy of 1 3 percent.
- the heating was cyclic during three working days averaging about 8 hours/cycle. Power was held to 4.7 1' .5 watts and resistance measured 0.065 :t 0.003 ohms. The fluctuations in the latter appear to be solely a function of the power and not of time. insofar is discernible with the accuracy of measurements.
- the left end of the bar consistently read 20 30 C higher than the right end.
- the bar is oblong shaped in cross section. Major axis inch; minor 4 inch. Hence cross sectional area is -3/32 sq. in. or 0.60 cm.
- the length between contacts is 2 inches or 5.1 cm.
- the resistivity is approximately:
- EXAMPLE 2 Tailings mud from the Oliver filters in a production operation is moved continuously to differential speed rollers on two paint mills in tandem, and mixed there with finely pulverized electrically conductive metal or metal ore, approximately 8 percent by volume on the total dry weight present, so as to achieve a resistivity of the final product of about 1 to 25 ohm cm.
- the material of the tailing mud has passed through the steps of crushing, comminuting to a fineness where a major percentage thereof passes through a 200 mesh screen, roasting, most conveniently in a rotary kiln, to remove volatiles and convert the less stable metal compounds to oxides, leaching with sulfuric acid to remove the monovalent metal constituent of the pyroxene, and separating tailings by flotation as discussed above.
- composition of tailings mud and conductive metal is then heated by any suitable means, preferably in vacuum, to a temperature between the melting point of the matrix material and of the metal. Temperatures of about 1,000 C l,200 C appear suitable. Addition of some leador alkali metal compounds in about 5 15 percent by weight further depress the fusion temperatures by up to several hundred degrees.
- the composition Prior to the final fusion, the composition may be pressed, cut, shaped or otherwise formed to the desired physical shape.
- the electrodes are applied prior to the final melting so that they will be intimately contacted with the metal network formed by mutually contacting metal particles within the product.
- electrodes can be applied subsequently, for example, by applying a solder layer with appropriate flux to the ends of the article, and soldering conductors to these. In some cases abrasion of the ends and subsequent compression application of electrodes may suffice.
- building blocks such as tiles or concrete blocks can be made suitable for resistance heating of a wall, or or even the entire inner walls, floors and ceilings of a structure.
- the compositions described herein can also be applied as pastes to ordinary concrete blocks or tiles before these are burned" in the kiln, so as to render them electrically heatable on the surface.
- a metal mixed mortar may be made to bridge the gap between bricks or blocks, so as to provide continuous conductivity. This may also serve as outside conductor to protect buildings from lightning.
- tailings employed for the purposes of this invention have a percentage analysis on dry basis within the following limits:
- Example l While the particular flotation mud employed in Example l was derived from a Spodumene, from which lithium had been extracted with dilute sulfuric acid, it is understood that other finely subdivided flotation muds can be equally employed, provided that they have been comminuted to a similar extent by any suitable means, such as ball milling, milling at hyper critical speeds by the process of Hukki, hammermilling, or the like. While this normally results in a fineness of the major portion of the product passing through a ZOO-mesh screen, and usually even a 325-mesh screen, this is not too critical, so long as the resultant flotation mud is easily intermixed with finely comminuted electrically conducting material to give a fairly uniform composition. The precise distribution of the particle size in the drilling mud used in not critical, because the finer particles will in any case coalesce in subsequent sintering or/and fusing steps.
- the roasting temperature is not critical so long as it adequately prepares the material for the action of the extraction medium to be used for removal of soluble constituents. Generally, addition of 4 to 30 percent by volume of the electrically conductive ingredient will be found suitable. When iron or steel filings are employed,
- the preferred range of electrically conductive ingredient is about 8 percent by volume.
- the resistivity is then usually about 0.1 to 25 ohm cm.
- the flotation mud described in Example 1 has a melting range below 1,200C. it may be convenient to work at still lower temperatures, and this becomes possible when additional melting point depressant substances are added, such as a substance selected from the following class: oxides, hydroxides and carbonates of lead and of alkali metals added in amounts of 4 35 percent by weight to the said flotation muds.
- additional melting point depressant substances such as a substance selected from the following class: oxides, hydroxides and carbonates of lead and of alkali metals added in amounts of 4 35 percent by weight to the said flotation muds.
- Binding agents such as silica dispersions may be employed to this end.
- a method of making an electrical heating element which comprises the combination of the steps of:
- tailings mud comprising by weight on a dry basis 40 to percent of silica, 10 to 20 percent of alumina and ID to 20 percent of calcia, and mixing said tailings mud with from 4 to 30 percent by volume of particles selected from iron and steel, forming said mixture into a pre-selected shape
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Resistance Heating (AREA)
- Conductive Materials (AREA)
Abstract
A heating element is cast, extruded or formed from a composition comprising finely comminuted ferrous metal in a matrix essentially consisting of a base composition consisting essentially of tailings muds from lithium ore extraction, comprising a major percentage of silicon, lesser percentages of aluminum and calcium, and to which some alkali metals or lead may be added in order to ease working and depress the melting point. An electrically conductive composition of controlled resistance is prepared in which the ferrous particles contact each other so as to give the resultant element resistivity of 10 3 to 1,000 Ohm centimeters. The tailings mud is a by-product from ore extraction, which is particularly suitable for this purpose because of its fine state of comminution, and its workability.
Description
United States Patent Dunn Dec. 2, 1975 HEATlNG ELEMENT, METHOD AND COMPOSITION [751 lnventor: Stanley Austin Dunn. Madison. Wis,
[73] Assignee: Bjorksten Research Laboratories,
Inc, Madison, Wis
[22] Filed: Dec. 3, I973 [211 Applt No: 421,073
Related U.S. Application Data [63] Continuation-impart of Ser. No. 242.436. April 10.
1972 abandoned [521 U.S. Cl. .1 219/345; 29/611129/621; 219/553; 252/513; 252/518; 252/512 [51] Int. Cl. a. F24H 9/02 [581 Field of Search 252/513 518; 29/611 345 [56] References Cited UNITED STATES PATENTS 2.855.491 10/1958 Navias 252/513 X 2,924,540 2/1960 D'Andrea 252/514 X 2,946 937 7/1960 Herbert 252/521 2,950,995 8/1960 Place ct a1. 252/518 X Primary E.t'amincrBenjamin R. Padgett Ari/stunt ExaminerE. Suzanne Parr Armrney. Age-m or FirmJohn M. Diehl; Johan Bjorksten [57] ABSTRACT A heating element is cast extruded or formed from a composition comprising finely comminuted ferrous metal in a matrix essentially consisting of a base composition consisting essentially of tailings muds from lithium ore extraction comprising a major percentage of silicon lesser percentages of aluminum and calcium, and to which some alkali metals or lead may he added in order to ease working and depress the melting point.
An electrically conductive composition of controlied resistance is prepared in which the ferrous particles contact each other so as to give the resultant clement resistivity of 10*" to 1,000 Ohm centimeters. The tailings mud is a by-product from ore extraction. which is particularly suitable for this purpose because of its fine state of comminution and its workability.
4 Claims. 6 Drawing Figures US. Patent Dec.2, 1975 HEATING ELEMENT, METHOD AND COMPOSITION BACKGROUND AND PRIOR ART withstanding ceramic bodies can be made by impreg- I nating a porous metal matrix with a ceramic compound which has a lower melting point than the metal. The importance of wetting the metal by the ceramic has been stressed (Grubel et al. U.S. Pat. Nos. 2,671,955 and 2,672,426). Furthermore, metals have been sintered together with lower melting conductive oxides to produce resistant contact surfaces (Ruben, U.S. Pat. No. 2,200,854). This last mentioned patent stresses the importance of electrical conductivity in the oxide, and limits claims to the conductive vanadium pentoxide.
In a prior patent application (Ser. No. 376,721), Applicant disclosed the production of electrically conductive thermal shock-resistant metal-ceramic compounds by the use of certain heat treatment cycles to cause cocrystallization of metal fragments at temperatures close to the sintering temperatures of said metals.
OBJECTS OF THE INVENTION An object of the invention is a superior composition for electrical heating, utilizing a waste material.
Another object is a method for preparing said composition, and heating elements made therefrom.
Further objects will appear from the following description.
BRIEF STATEMENT OF THE INVENTION A low cost product, heatable by electrical resistance to temperatures suitable for radiant heating of human dwellings and other applications calling for moderate temperature (from slightly elevated to about 150C) is prepared by mixing a finely comminuted electrically conductive particulate substance with a flotation mud from an ore refining process said mud comprising silica-alumina-calcia type tailings after milling, roasting and extracting; and compacting the resultant product so as to secure the desired electrical resistance for resistance heating, and stabilizing it, for example, by one or more of the following operations: further drying, compacting, sintering, or fusion and enameling steps.
THE DRAWINGS Reference is made to the drawings, of which:
FIG. 1, FIG. 2, and FIG. are enlarged cross-sectional views.
FIG. 3 and FIG. 4 are cross-sectional views.
FIG. 6 is a perspective view.
DETAILED STATEMENT OF THE INVENTION Referring to the drawings, FIG. 1 illustrates a magnified (about X) section through a dispersion of conductive ore or metal fragments or particles in a matrix of fused flotation mud taken from the continuous vacuum (Oliver") filters, removing flotation mud from a process resulting in flotation tailings being formed following ore treating steps including milling, roasting, extracting and flotation.
This composite is referred to in the drawings as l0.
The essential points are that the tailings used as raw material be finely comminuted, roasted, to remove volatiles and converted, as much as possible based on the raw material, to an oxide form suitable for glass formation. Subsequent leaching has removed the wateror acid-solubles. After the final flotation process, vacuum filtration removes the major percentage of water, thus leaving a pasty product in a form easily and economically handled and excellently suitable for blending with iron filings, crushed conductive metal ores, or oxides of ferrous or other ores reducible to conductive metal by treatment with reducing agents of which hydrogen, car bon monoxide, and hydrocarbon gases are the most convenient and inexpensive.
The blending can be done on conventional blending equipment, such as, for example, continuous ribbon mixers such as Day double spiral ribbon mixers, or in sigma blade mixers, but most economically by multiple pass through differential speed rollers on a paint mill.
Subsequent drying and sintering and particularly fu sion at about l,000 1,200 C leaves the conductive particles 2 scattered, enclosed in matrix I, to such extent that they are protected from oxidation by atmospheric oxygen when resistance heated at normal operating temperatures for residential heating panels, say at about to l50 C. The density and form of the suspended conductive particles are such that these frequently touch each other.
In FIG. 2 the melt has been kept 3 hours at 1,200, with very slow stirring (stirrer at about 5 revolutions per hour) so that some coalescence or co-crystallization of the particles has taken place, augmenting thereby the contact between particles and resulting in a more feathery structure, 3.
FIG. 3 shows an embodiment in which the matrix is very thick, for example, like a brick or a concrete block 5, or other conventional building elements and the particles have been introduced only in a layer of about a couple mils to 36 inch, so that the building elements can be assembled and then heated by electric current conducted only through the thin layer. The particles can be introduced, for example, by projecting them into the still soft mass at high velocity by spraying or centrifugal throwing, with optional subsequent application of an enamel, or a sealing coat, for example, of soluble silica or silicate solution such as sodium silicate, or colloidal silicic acid solutions.
FIG. 4 shows such a building element in which the main body is free from metal and has been foamed, for example, by inclusion of a gas forming sulfide or carbonate in the mix as well known in the art. 4 indicates bubbles, l0 the metal carrying conductive layer.
FIG. 5 is a magnified detail view, showing a surface sealing layer 6 of enamel, silicate, or the like, to close such cracks as might form and enhance the resistance of the element to oxidation. It may also serve decorative purposes.
FIG. 6 shows a perspective view of a heating element in panel form. 7 is the heating surface, 8 the electrodes attached thereto in any of the many manners known to the art. Preferably the electrode surface is applied before any sealant coat. The electrodes may be simply clamped firmly over the surface, or the surface may be first specially prepared by abrading and fusing over it a solder with appropriate flux to better bind the electrode. Since the art in this field is voluminous and throughly known, I believe further discussion of this aspect to be superfluous.
EXAMPLE 1 A heating rod was made from the tailings mud from spodumene, a lithium aluminum silicate mineral, LiAl(SiO belonging to the pyroxene group, from which the lithium had been extracted by the steps of crushing, ballmilling 4 hours, roasting in a rotary kiln. cooling, extracting with dilute sulfuric acid. washing, froth flotation, and separation of the finely divided (over 50 percent through 325 mesh screen) wet mud on a rotary vacuum filter (Oliver filter). The tailings mud used in this experiment was a composite of four samples, and had the following analysis:
This tailings mud was dried. and the resulting powder was mixed with volume percent of iron filings. The mixed powders were ballmilled together over night, and 17.5 grams were placed in a graphite mold 6 inches long by 56 inch wide and as inch deep of U-shaped cross section. The mold and powders were placed in a vacuum furnace, the pressure was reduced to below 10 Torricelli and the temperature raised.
This was repeated four times, the temperature being raised to successively higher values each time. The first time a temperature of 450 C was reached over 6 hours; the sample lost 0.25 gm. weight. The second heat was to 660 C in 5 hours; the third to 890 C in 5 hours. In the latter instance the sample was fused over most ofits length, a little of its initial powdery nature being discernible at one end. The final heat to 940 C lasted for 7 hours. The sample was fused over its entire length.
A half inch of each end of one 3 inch length of the above was painted with conductive silver paint, the remainder with Na siO solution and the coatings dried. Electrodes were attached to the silvered ends and the bar was subjected to several cycles of electrical heating to temperatures between 100 and 140 C.
Temperatures were measured with thermally insulated chromel alumel thermocouples made of fine wires (0.005 inch dia.) electrically insulated from the heater bar by l/32 inch thick piece of boron nitride and recorded on a chart recorder. Current through. and potential across the bar were measured to an accuracy of 1 3 percent.
The heating was cyclic during three working days averaging about 8 hours/cycle. Power was held to 4.7 1' .5 watts and resistance measured 0.065 :t 0.003 ohms. The fluctuations in the latter appear to be solely a function of the power and not of time. insofar is discernible with the accuracy of measurements.
The left end of the bar consistently read 20 30 C higher than the right end. The bar is oblong shaped in cross section. Major axis inch; minor 4 inch. Hence cross sectional area is -3/32 sq. in. or 0.60 cm. The length between contacts is 2 inches or 5.1 cm. Thus, the resistivity is approximately:
0.6 cm R Z (.005 I .003) Ohm 5.1 cm .0077 t .0004 ohm cm (7.7 1.41) i 10" ohm cm under the above conditions.
EXAMPLE 2 Tailings mud from the Oliver filters in a production operation is moved continuously to differential speed rollers on two paint mills in tandem, and mixed there with finely pulverized electrically conductive metal or metal ore, approximately 8 percent by volume on the total dry weight present, so as to achieve a resistivity of the final product of about 1 to 25 ohm cm. Prior to this step the material of the tailing mud has passed through the steps of crushing, comminuting to a fineness where a major percentage thereof passes through a 200 mesh screen, roasting, most conveniently in a rotary kiln, to remove volatiles and convert the less stable metal compounds to oxides, leaching with sulfuric acid to remove the monovalent metal constituent of the pyroxene, and separating tailings by flotation as discussed above.
The composition of tailings mud and conductive metal is then heated by any suitable means, preferably in vacuum, to a temperature between the melting point of the matrix material and of the metal. Temperatures of about 1,000 C l,200 C appear suitable. Addition of some leador alkali metal compounds in about 5 15 percent by weight further depress the fusion temperatures by up to several hundred degrees.
Prior to the final fusion, the composition may be pressed, cut, shaped or otherwise formed to the desired physical shape.
If the end product is to be a heater, the electrodes are applied prior to the final melting so that they will be intimately contacted with the metal network formed by mutually contacting metal particles within the product. Alternatively, electrodes can be applied subsequently, for example, by applying a solder layer with appropriate flux to the ends of the article, and soldering conductors to these. In some cases abrasion of the ends and subsequent compression application of electrodes may suffice.
[n this manner large surface heating panels can be produced at a very low cost, using as the principal raw material tailings which would otherwise represent a difficult disposal problem.
As pointed out above, it is possible to render only the surface of a heavy body conductive in the manner indicated and to confine the conductivity to any desired part thereof. Thus, building blocks such as tiles or concrete blocks can be made suitable for resistance heating of a wall, or or even the entire inner walls, floors and ceilings of a structure. The compositions described herein can also be applied as pastes to ordinary concrete blocks or tiles before these are burned" in the kiln, so as to render them electrically heatable on the surface. A metal mixed mortar may be made to bridge the gap between bricks or blocks, so as to provide continuous conductivity. This may also serve as outside conductor to protect buildings from lightning.
Generally, the tailings employed for the purposes of this invention have a percentage analysis on dry basis within the following limits:
so, 55 mp, 15 :5 C210 15 :5
If it is desired to further lower the melting point of the matrix employed, we find it convenient to lower this by the addition of 4 to 35 percent by weight of a substance comprising at least one member of the class consisting of leadand alkali metalcarbonates, oxides and hydroxides.
While the particular flotation mud employed in Example l was derived from a Spodumene, from which lithium had been extracted with dilute sulfuric acid, it is understood that other finely subdivided flotation muds can be equally employed, provided that they have been comminuted to a similar extent by any suitable means, such as ball milling, milling at hyper critical speeds by the process of Hukki, hammermilling, or the like. While this normally results in a fineness of the major portion of the product passing through a ZOO-mesh screen, and usually even a 325-mesh screen, this is not too critical, so long as the resultant flotation mud is easily intermixed with finely comminuted electrically conducting material to give a fairly uniform composition. The precise distribution of the particle size in the drilling mud used in not critical, because the finer particles will in any case coalesce in subsequent sintering or/and fusing steps.
The roasting temperature is not critical so long as it adequately prepares the material for the action of the extraction medium to be used for removal of soluble constituents. Generally, addition of 4 to 30 percent by volume of the electrically conductive ingredient will be found suitable. When iron or steel filings are employed,
we usually find the preferred range of electrically conductive ingredient to be about 8 percent by volume. The resistivity is then usually about 0.1 to 25 ohm cm.
In adding the conductive component, I find it advantageous to work roughly with the folloqing percentage composition lron l0 20% by weight Silica 35 60% by weight Alumina 5 l5% by weight Calcia l0 15% by weight The balance to make I00 percent, where indicated, will consist of secondary percentages of compounds of bound iron, magnesia, sulfur, carbon, phosphorus, manganese, titanium, sodium, potassium, and lead. The three last mentioned, in particular, may be added to depress the melting point of the matrix, in quantities of about 5 15 percent.
The flotation mud described in Example 1 has a melting range below 1,200C. it may be convenient to work at still lower temperatures, and this becomes possible when additional melting point depressant substances are added, such as a substance selected from the following class: oxides, hydroxides and carbonates of lead and of alkali metals added in amounts of 4 35 percent by weight to the said flotation muds.
In some instances, particularly when the desired form of an article renders fusing undesirable, we may employ drying with subsequent compression to achieve form stability. Binding agents such as silica dispersions may be employed to this end.
Having thus described my invention, 1 claim:
1. A method of making an electrical heating element which comprises the combination of the steps of:
providing a tailings mud comprising by weight on a dry basis 40 to percent of silica, 10 to 20 percent of alumina and ID to 20 percent of calcia, and mixing said tailings mud with from 4 to 30 percent by volume of particles selected from iron and steel, forming said mixture into a pre-selected shape,
firing said pre-sel'ected shape at from about 940 C.
to about l,200 C. to cause said mixture to coalesce,
cooling and resultant article,
abrading portions of the article to which electrodes are to be attached, and
attaching electrodes to said abraded areas to provide said electrical heating element.
2. The electrical element of claim 1, said element having the form of a flat panel.
3. The product of the process of claim I.
4. The product of the process of claim 2.
i 1 I i i
Claims (4)
1. A METHOD OF MAKING AN ELECTRICAL HEATING ELEMENT WHICH COMPRISES THE COMBINATION OF THE STEPS OF: PROVIDING A TAILINGS MUD COMPRISING BY WEIGHT ON A DRY BASIS 40 TO 70 PERCENT OF SILICA, 10 TO 20 PERCENT OF ALUMINA AND 10 TO 20 PERCENT OF CALCIA; AND MIXING SAID TAILINGS MUD WITH FROM 4 TO 30 PERCENT BY VOLUME OF PARTICLES SELECTED FROM IRON AND STEEL, FORMING SAID MIXTURE INTO A PHE-SELECTED SHAPE, FIRING SAID PHR-SELECTED SHAPE AT FROM ABOUT940*C. TO ABOUT 1,200*C. TO CAUSE SAID MIXTURE TO COALESCE, COOLING AND RESULTANT ARTICLE, ABRADING PORTIONS OF THE ARTICLE TO WHICH ELECTRODES ARE TO BE ATTACHED, AND ATTACHING ELECTRODES TO SAID ABRADED AREAS TO PROVIDE SAID ELECTRICAL HEATING ELEMENT.
2. The electrical element of claim 1, said element having the form of a flat panel.
3. The product of the process of claim 1.
4. The product of the process of claim 2.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US421073A US3924098A (en) | 1972-04-10 | 1973-12-03 | Heating element, method and composition |
US05/636,973 US4015105A (en) | 1973-12-03 | 1975-12-02 | Panel electrical heating element |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US24243672A | 1972-04-10 | 1972-04-10 | |
US421073A US3924098A (en) | 1972-04-10 | 1973-12-03 | Heating element, method and composition |
Related Parent Applications (1)
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US05376721 Continuation-In-Part | 1974-06-22 |
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Application Number | Title | Priority Date | Filing Date |
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US05/636,973 Continuation-In-Part US4015105A (en) | 1973-12-03 | 1975-12-02 | Panel electrical heating element |
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US3924098A true US3924098A (en) | 1975-12-02 |
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US421073A Expired - Lifetime US3924098A (en) | 1972-04-10 | 1973-12-03 | Heating element, method and composition |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4015105A (en) * | 1973-12-03 | 1977-03-29 | Bjorksten Research Laboratories, Inc. | Panel electrical heating element |
WO1981003238A1 (en) * | 1980-04-30 | 1981-11-12 | J Lee | Resistant heat generating element and method of manufacturing same |
US4505803A (en) * | 1981-06-04 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4505783A (en) * | 1981-05-25 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector and method of using same |
US4505802A (en) * | 1981-05-25 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4505804A (en) * | 1981-06-04 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4505805A (en) * | 1981-06-04 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4541898A (en) * | 1981-05-25 | 1985-09-17 | Ngk Insulators, Ltd. | Method for heating |
US10912154B1 (en) * | 2020-08-06 | 2021-02-02 | Michael E. Brown | Concrete heating system |
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US2855491A (en) * | 1954-06-30 | 1958-10-07 | Gen Electric | Metal-ceramic electrical resistors |
US2924540A (en) * | 1958-05-23 | 1960-02-09 | Du Pont | Ceramic composition and article |
US2946937A (en) * | 1956-05-07 | 1960-07-26 | Plessey Co Ltd | Ceramic material and method of producing the same |
US2950995A (en) * | 1957-03-18 | 1960-08-30 | Beckman Instruments Inc | Electrical resistance element |
-
1973
- 1973-12-03 US US421073A patent/US3924098A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US2855491A (en) * | 1954-06-30 | 1958-10-07 | Gen Electric | Metal-ceramic electrical resistors |
US2946937A (en) * | 1956-05-07 | 1960-07-26 | Plessey Co Ltd | Ceramic material and method of producing the same |
US2950995A (en) * | 1957-03-18 | 1960-08-30 | Beckman Instruments Inc | Electrical resistance element |
US2924540A (en) * | 1958-05-23 | 1960-02-09 | Du Pont | Ceramic composition and article |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4015105A (en) * | 1973-12-03 | 1977-03-29 | Bjorksten Research Laboratories, Inc. | Panel electrical heating element |
WO1981003238A1 (en) * | 1980-04-30 | 1981-11-12 | J Lee | Resistant heat generating element and method of manufacturing same |
US4505783A (en) * | 1981-05-25 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector and method of using same |
US4505802A (en) * | 1981-05-25 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4541898A (en) * | 1981-05-25 | 1985-09-17 | Ngk Insulators, Ltd. | Method for heating |
US4505803A (en) * | 1981-06-04 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4505804A (en) * | 1981-06-04 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US4505805A (en) * | 1981-06-04 | 1985-03-19 | Ngk Insulators, Ltd. | Oxygen concentration detector |
US10912154B1 (en) * | 2020-08-06 | 2021-02-02 | Michael E. Brown | Concrete heating system |
US11683862B2 (en) | 2020-08-06 | 2023-06-20 | Michael E. Brown | Concrete heating system |
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