US2906632A - Oxidation resistant articles - Google Patents

Oxidation resistant articles Download PDF

Info

Publication number
US2906632A
US2906632A US683111A US68311157A US2906632A US 2906632 A US2906632 A US 2906632A US 683111 A US683111 A US 683111A US 68311157 A US68311157 A US 68311157A US 2906632 A US2906632 A US 2906632A
Authority
US
United States
Prior art keywords
oxidation
percent
phosphate
carbon
invention
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.)
Expired - Lifetime
Application number
US683111A
Inventor
John D Nickerson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Priority to US683111A priority Critical patent/US2906632A/en
Application granted granted Critical
Publication of US2906632A publication Critical patent/US2906632A/en
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522Graphite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00Clay-wares
    • C04B33/02Preparing or treating the raw materials individually or as batches
    • C04B33/13Compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00Clay-wares
    • C04B33/02Preparing or treating the raw materials individually or as batches
    • C04B33/13Compounding ingredients
    • C04B33/1315Non-ceramic binders
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5076Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
    • C04B41/5092Phosphate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02Apparatus characterised by their chemically-resistant properties
    • B01J2219/025Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0272Graphite

Description

Sept. 29, 1959 J. D. NICKERSON 2,906,532

OXIDATION RESISTANT ARTICLES Filed Sept. 10, 1957 3 Sheets-Sheet 1 -23-4274 DRY PICKUP 75oc. 7 B 4-3IZ DRY PICKUP 675C. 5 -5212 DRY PICKUP 650C.

% WT. Loss I'lme Hrs.

I5 I I I I I I I I F A-AMMONIUM PHOSPHATE 6-92 DRY PICKUP B-ZINC PHOSPHATE GLASS TREAT 5-22 DRY PICKUP BL-ZINC PHOSPHATE GLASS TREAT IO'BZ DRY PICKUP B-ZINC PHOSPHATE GLASS TREAT 42-92 DRY PICKUP C-PRIOR ART F-CONTROL GALUMINUM PHosPHATE 7-8ZASH a 6 l I l Bl L 10 2o so so so '90 Time Hrs. INVENTOR.

A. i a 9 A J. DAVID NICKERSON A T TORNEY Sept. 29, 1959 c sc'N 2,906,632

OXIDATION RESISTANT ARTICLES Filed Sept. 10, 1957 3 Sheets-Sheet 2 I I I8 ,CONTROL I /PHOSPHORUS SILICON DIOXIDE I l l2 5, I %RIOR ART 3 10 V 2- I g 8 I x zmc PHOSPHATE GLASS 2 o k 0 2 4 s a 10 I2 I4 I6 18 2o 22 24 3 Time Hrs.

BZlNC PHOSF HATE GLA'SS 9 5-22 DRY PICKUP 650 c. BZINC PHOSPHATE GLASS 0 a 6-42 DRY PICKUP 750 c.

B -ZINC PHOSPHATE GLASS 14-12mm PICKUP 750C. 1 7 -GALUM|NUM PHOSPHATE ssoc.

G-ALUMINUM PHOSPHATE 7so'c. e ,5" (I) O 5 I l 3 4 V I x l 042'4 6 8 IO I2 I4 16 18202224 Time Hrs. gf- 4 INVENTOR.

J. DAVID NICKERSON ATTORNEY Sept. 29, 1959 J. D. NICKERSON 2,906,532

- I OXIDATION RESISTANT ARTICLES Filed Sept. 10. 1957 3 Sheets-Sheet 3 Wt Loss 25 5O 75 I00 I I I 200 225 Time-Minutes A IN VEN TOR.

Z yj J. DAVID NICKERSON ATTORNEY omnArroN RESISTANT ARTICLES John D. Nickerson, Lakeland, Fla.', assignor to Union Carbide Corporation, a corporation of New York Application September 10, 1957,; Serial No. 683,111 3Claims.- (Cl. 106-5 This invention relates to methods for rendering carbonaceous articles oxidation resistant. More specifically, the invention relates to methods of providing zinc phosphate compounds in carbon and graphite bodies to render such bodies resistant to oxidation at temperatures upwards of 600 C.

Because of the frequent uses made of carbon and I retardants have been diverse phosphorus-containing come pounds. Thus prior art has amply taught that phosphoric acid tends to increase the oxidation resistance of carbonaceous bodies. It has been found also that many organic'phosphates as well as the phosphate salts of sodium, aluminum, calcium, potassium and magnesium are eifective oxidation reducing additives. In general, however, methods of protection, depending upon the above-mentioned additives, are neither exceptionally effective nor long lasting in effect.

Bearing in mind the above outlined limitations of prior art attempts to render'carbon and graphite bodies oxidation resistant, the primary object of the present invention is to provide improved methods for rendering such articles oxidation resistant at temperatures up to 950 C.

An equally important object of the invention is to provide articles composed of carbon and graphite, which possess improved resistance to oxidizing conditions at temperatures up to 950 C. Y

A further object of'the invention is to provide zinc phosphate compounds in carbon parts, which compounds serve to maintain the original dimensions of such parts despite loss of weight by the same.

These and other objects and advantages of the invention will become apparent as the description thereof proceeds, particularly when taken in connection with the accompanying drawing in which:

Fig. 1 is a graphical representation relating the effects of temperature on the oxidation rates of samples treated in accordance with the method of the invention; and

Figs.. 2, 3, 4, and are graphical representations comparing the oxidation rates of samples treated following the method of the invention with those of samples treated with various prior art oxidation retardants.

The foregoing and related objects of the invention are attained by providing in carbon and graphite articles a composition consisting of a zinc phosphate compound or glass. The reagents required to form the zinc phosphate compound may be introducedinto formed bodies by soaking or impregnation procedures, or may be incorporated, in their simple or combined form, in the green carbon mix.

The elfective product of the. composition is a very viscous liquid, which wets unoxidized carbon surfaces,

and spreads through the carbon matrix to provide a barrier between the carbon and the surrounding atmosphere. This barrier provides long lasting and efiicient oxidation protection at temperatures ranging from 500 C. to 950? C. In the practice of the invention, articles, the protection of which is desired, may be pre-heated to form a phosphate glass, or the glass may be allowed to form during service.

Best results are obtained in the practice of the invention when the weight ratios of forming agents; namely,

ammonium phosphate, zinc chloride and boric acid are in the range of 4:1:0 and 222:0.25. The boron constituent may be omitted to give compositions about 20 percent superior to those given by compositions containing boron at temperatures of 725 C. to 750 C. At 675 C., however, such a composition will be about 10 percent less effective than when boron is present. Above 750 C., the differences in oxidation rates between the two are not significant. In effect, by varying the ratio of constituents and other features of the present invention, 'it is possible to obtain greater protection at a given temperature than at other temperatures above or below the given value, as will be disclosed more fully her einafter.

In one embodiment of the invention, a shaped or amorphous carbon or graphite body is treated with an aqueous acid solution containing zinc phosphate-forming agents present in an amount ranging from 20 percent to percent by weight. Depending upon the type of carbon or graphite stock involved, and the amount of retardant pick-up desired, the articles may be dipped in the solution or vacuum impregnated. Multiple treatments provide additional pick-up to desiredhigher levels. Treated articles may be dried at 110 C. or at' room temperature, if time permits. A slow drying procedure is preferred because of the tendency of treated stock to sweat when rapidly heated.

Agents suitable for the practice of the invention inphosphorus such as monobasic ammonium phosphate,

'- samples of graphite.

and bore-phosphoric acid (BPO .H O). Alternatively, boric acid may be used with the above compounds. In the preferred embodiment of the invention, best results are obtained when monobasic ammonium phosphate, zinc chloride and boric acid are used in the molar ratio 321:0.25. These constituents are dissolved in the order: boric acid; ammonium phosphate; and zinc chloride; in a 1.5 percent solution hydrochloric acid, employing great care to insure that each individual constituent is entirely dissolved prior to the addition of the next. The solution is kept acid to prevent the precipitation of zinc phosphate. Preferably about 0.1 percent of a commercially available wetting agent should be added to the solution to speed the penetration thereof into carbon or graphite pores. In a specific example of the invention a 30 percent solution by weight containing the above weight ratio of the agents was admitted to a previously evacuated vessel containing a number 'of'l inch x 1 inch x /2 inch Four to 5 percent dry pick-up of solution was observed after one impregnation, and it-was possible to obtain an 8 to 9 percent pick-up without forming a white coating on the articles. In another example of the invention, 20 inch x 72 inch thermic electrodes were dipped for 30 seconds in the same solution as above indicated, and an 0.5 percent dry pick-up was observed.v

In each case the dry samples exhibited no hygroscopicity.

Table I compares the performance of treated and-1m treated samples at 500 C.

-Uncured reiersto the series oi operations of lmpregnatingwith the solution; drylng'at 100 C. and then oxidizing'at 500 C.

2 Cured" refers to the series o'ioporatlons'ii impregnating, drying at 100 0., heating under nitrogen to 700 C. and then oxidizing at 500 0.

Where large initial weight losses occurred due to volatile components of the treat, these weights have been subtracted from the total loss to give the oxidation losses listed above.

In Table II below are shown typical oxidation results obtained with graphite samples impregnated with solutionscontaining indicated weight ratios of reagents, monobasic ammonium phosphate, zinc chloride and boric acid, respectively.

TABLE H Oxidation at 675 C.

Percent Percent loss after Sample No. Ratio of reagents pick-up Z'hours 19 hours In a further embodiment of the invention zinc-phosphate-forming agents were added directly to the green carbonaceous mix. In typical examples of this embodiment, zinc chloride and'boro-phosphoric acid were added in amounts from 4' to 20' parts per 100 in the aggregate, to green mixes formed by commingling 75 percent by weight of carbon flour, 25 percent by weight of coke; and 34 parts per 1000f coal tar pitch melting at around 120" C. Table III below shows the results obtained with baked carbon stock containing the indicated amounts of zinc phosphate compound. 7

TABLE HI Oxidation temperature 725 C.

' Quantity of additive in p.p.h. Percent oxidation loss after-- Zn'Clj. BPO4.H}O HQBO: 1hr. 2hrs. 4hrs.

; 2'. 2 2.5 14.5 33 6 6 1.8 9.6 18 2.. 2 1.7 9.2 14 6., 14 1.6 8.1 ControL--- 2.3 17 31.1

In: another. variant of the'invention', reaction products formed at high temperatures by various zinc phosphateforming agents were added to the green carbon mix. Table IV below shows the results of adding the reaction product formed at 500 C. by mono-basic ammonium phosphate,- zinc chloride and boric acid to a green mix consisting of 75. percent carbon fiour, 25 percent coke flour, and 34 parts per 100 of coal tar pitch binder. The reactionproduct was added in a crushed form such that it passed through a 100 mesh screen.

TABLE IV Oxidation temperature 600 C.

Percent loss after- }4 hr. 1 hr. 2 hrs. 5 hrs. 19 hrs.

a. a 8.1 11. 0 14. 2 31.1 a o '5. 9 10.6 21. 9 2.4 8.4. I 17.1 34.1

A still further modification of the-invention is based'on the discovery thatzinc-chloride and ammonium phosphate, or zinc chloride and boro-phosphoric acid provide excellent oxidation protection if the treated samples are pre-heated, preferably in a non-oxidizing atmosphere, to 800 C. to 900 C., respectively. This. pre-heatingx is required to promote reaction and form a. protecting medium of suitablecharacteristics to permeate the matrix.

The exact mechanism. whereby the beneficial eifects of the invention are attained is not knownexactly. However, it has been noted that the formation of the protective glass medium takes place in three discrete steps:

(1) Between 200 C; and 500 C., the reagents react with the evolution of ammonium chloride and hydrogen chloride. This reaction. is. accompanied by. a spreading of the reactants over the exposed surface of the carbon or graphite article.

(2) Between 500 C. and 700 C.,, the reaction product changes to a very viscousliquidwhichwets the=carbon and. forms a barrier against oxidation. Upon cooling, the mass is crystalline,v and. the phosphate can. be identified by diffraction techniques. The type of phosphate formed naturally dependsupon the relativcproportionsof reactants.

(3') Above 650 C. to 700 C.,.a reaction oi thezinc phosphate compound occurs such that upon cooling, the mass resembles a glass. It has been observed that at 650 C. the very viscous zincphosphate glass causes a secondary bonding to the treated. material. Even after 50 per cent weight loss of the carbon or graphite sample, the. original dimensions of the unoxidized sample are not effected. Through its wetting action and very viscous natureat that temperature: the glass serves as a bond between what normally would have become adiscontinuous carbon phase at that weight loss level. This bond serves as: av means of maintaining the dimensions of treatedparts, and of prolonging stock are in the case of molds and chill trays.

Referring now to the drawing, Figure 1 shows the eifect of temperature upon the oxidation rate of samples which have been impregnated to the dry pickups indicated' with av 2:1:0.25 ammonium phosphate, zinc chloride and boric acid solution. The graph showsthat there is approximately a two-fold increase in oxidation rate. upon going from 650 C. to 675 C. Also indicated is the fact that the-axidationrate of stock. treated inthe manner of the invention at 750 C. iscomparable to the control rate at 650 C.

In' Figure 2 are given comparisons between the glass of the invention and other oxidation retardants. as listed. The curve which is labeled C is a. sample of stock impregnated with calcium phosphate and/or magnesium phosphate. The discerning feature isthe change inrate of the various plots. The method of the invention treat is observed to be more enduring than other methods, and its advantage over ammonium phosphate is very apparent. Thus, it can be seenthat the method'of the invention protection is more enduring and more effective than the protection obtained by other procedures.

Figure 3" gives a further comparison between various treats and the present method at- 675 C.

Figure 4 is a comparison between aluminum phosphate and the present additives at" 650 C; and 750 C.

for equivalent quantities of ash, G and B" should be compared at 750 C. a

In Figure 5 are shown the results of oxidation tests at 900-925 C. run on samples impregnated with the 2:1:0.25 composition as compared to a sample of aluminum phosphate and a sample in which born-phosphoric acid has been substituted for boric acid. The samples of treated stock in all cases exhibit lower initial rates of oxidation than does the control. However, after seventyfive minutes, the rate of treated stock raises to that of the control.

What is claimed is:

1. An oxidation resistant article consisting of a carbonaceous matrix selected from the group consisting of carbon and graphite, having from about 4 percent to about 20 percent by weight thereof of a zinc phosphate composition comprising essentially ammonium phosphate, zinc chloride and boric acid in the ratios of between 4:1:0 and 21220.25.

2. A process for producing oxidation resistant car- 20 bonaceous articles consisting in placing from about 4 to about 20 percent by weight of a zinc phosphate composition in the pores of said articles, said composition con sisting essentially of at least one phosphorus-containing compound selected from the group consisting of the oxy acids of phosphorus and the ammonium salts of phosphorus, a-zinc halide, and boric acid, the rate ratio of said compounds being between 2:1:0 and 2:2:0.25.

3Q An oxidation-resistant article consisting of a carbonaceous matrix selected from the group consisting of graphite and carbon, and having therein from about 4 percent to about 20 percent by weight of a composition consisting essentially of a phosphorus-containing agent selected from the group consisting of the oxy acids of phosphorus and the ammonium salts of phosphorus, together with a zinc halide and a boric acid, the weight ratios of said materials ranging between 2:1:0 and 2:2:0.25.

References Cited in the file of this patent UNITED STATES PATENTS 2,685,541 Woodburn et al. Aug. 3, 1954

Claims (1)

  1. 3. AN OXIDATION-RESISTANT ARTICLE CONSISTING OF A CARBONACEOUS MATRIX SELECTED FROM THE GROUP CONSISTING OF GRAPHITE AND CARBON, AND HAVING THEREIN FROM ABOUT 4 PERCENT TO ABOUT 20 PERCENT BY WEIGHT OF A COMPOSITION CONSISTING ESSENTIALLY OF PHOSPHORUS-CONTAINING AGENT SELECTED FROM THE GROUP CONSISTING OF THE OXY ACIDS OF PHOSPHORUS AND THE AMMONIUM SALTS OF PHOSPHORUS, TOGETHER WITH A ZINC HALIDE AND A BORIC ACID, THE WEIGHT RATIOOS OF SAID MATERIALS RANGEING BETWEEN 2:1:0 AND 2:2:0:25.
US683111A 1957-09-10 1957-09-10 Oxidation resistant articles Expired - Lifetime US2906632A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US683111A US2906632A (en) 1957-09-10 1957-09-10 Oxidation resistant articles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US683111A US2906632A (en) 1957-09-10 1957-09-10 Oxidation resistant articles
DEU5576A DE1131586B (en) 1957-09-10 1958-09-02 Process for improving the Oxydationswiderstandsfaehigkeit of carbonaceous articles

Publications (1)

Publication Number Publication Date
US2906632A true US2906632A (en) 1959-09-29

Family

ID=24742617

Family Applications (1)

Application Number Title Priority Date Filing Date
US683111A Expired - Lifetime US2906632A (en) 1957-09-10 1957-09-10 Oxidation resistant articles

Country Status (2)

Country Link
US (1) US2906632A (en)
DE (1) DE1131586B (en)

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065088A (en) * 1959-09-30 1962-11-20 Union Carbide Corp Oxidation-resistant graphite article and method
US3342627A (en) * 1964-05-05 1967-09-19 Pure Carbon Company Inc Method for impregnating graphite bodies and the article produced therefrom
US3351477A (en) * 1966-01-27 1967-11-07 Union Carbide Corp Treat solution for rendering carbonaceous articles oxidation resistant
US3804648A (en) * 1970-12-11 1974-04-16 Ici Ltd Graphite compositions
US4439491A (en) * 1982-11-18 1984-03-27 Great Lakes Carbon Corporation Oxidation retardant for graphite
US4530853A (en) * 1984-06-06 1985-07-23 Great Lakes Carbon Corporation Non-conducting oxidation retardant coating composition for carbon and graphite
US4617232A (en) * 1982-04-15 1986-10-14 Kennecott Corporation Corrosion and wear resistant graphite material
US4621017A (en) * 1982-04-15 1986-11-04 Kennecott Corporation Corrosion and wear resistant graphite material and method of manufacture
US4726995A (en) * 1985-11-13 1988-02-23 Union Carbide Corporation Oxidation retarded graphite or carbon electrode and method for producing the electrode
US5401440A (en) * 1993-01-13 1995-03-28 The B. F. Goodrich Company Inhibition of catalyzed oxidation of carbon-carbon composites
US5759622A (en) * 1994-03-18 1998-06-02 The B.F. Goodrich Company Method of inhibiting catalyzed oxidation of carbon-carbon composites
US6551709B1 (en) 1994-03-18 2003-04-22 Goodrich Corporation Methods of inhibiting catalyzed oxidation of carbon-carbon composites using phosphoric acid, a zinc salt, and an aluminum salt and articles made therefrom
US20090269191A1 (en) * 2002-07-12 2009-10-29 Cooper Paul V Gas transfer foot
US7906068B2 (en) 2003-07-14 2011-03-15 Cooper Paul V Support post system for molten metal pump
US8075837B2 (en) 2003-07-14 2011-12-13 Cooper Paul V Pump with rotating inlet
US8178037B2 (en) 2002-07-12 2012-05-15 Cooper Paul V System for releasing gas into molten metal
US8337746B2 (en) 2007-06-21 2012-12-25 Cooper Paul V Transferring molten metal from one structure to another
US8366993B2 (en) 2007-06-21 2013-02-05 Cooper Paul V System and method for degassing molten metal
US8444911B2 (en) 2009-08-07 2013-05-21 Paul V. Cooper Shaft and post tensioning device
US8449814B2 (en) 2009-08-07 2013-05-28 Paul V. Cooper Systems and methods for melting scrap metal
US8524146B2 (en) 2009-08-07 2013-09-03 Paul V. Cooper Rotary degassers and components therefor
US8529828B2 (en) 2002-07-12 2013-09-10 Paul V. Cooper Molten metal pump components
US8535603B2 (en) 2009-08-07 2013-09-17 Paul V. Cooper Rotary degasser and rotor therefor
US8613884B2 (en) 2007-06-21 2013-12-24 Paul V. Cooper Launder transfer insert and system
US8714914B2 (en) 2009-09-08 2014-05-06 Paul V. Cooper Molten metal pump filter
US8923360B2 (en) 2010-07-01 2014-12-30 Graftech International Holdings Inc. Graphite electrodes
US9011761B2 (en) 2013-03-14 2015-04-21 Paul V. Cooper Ladle with transfer conduit
US9108244B2 (en) 2009-09-09 2015-08-18 Paul V. Cooper Immersion heater for molten metal
US9156087B2 (en) 2007-06-21 2015-10-13 Molten Metal Equipment Innovations, Llc Molten metal transfer system and rotor
US9205490B2 (en) 2007-06-21 2015-12-08 Molten Metal Equipment Innovations, Llc Transfer well system and method for making same
US9409232B2 (en) 2007-06-21 2016-08-09 Molten Metal Equipment Innovations, Llc Molten metal transfer vessel and method of construction
US9410744B2 (en) 2010-05-12 2016-08-09 Molten Metal Equipment Innovations, Llc Vessel transfer insert and system
US9643247B2 (en) 2007-06-21 2017-05-09 Molten Metal Equipment Innovations, Llc Molten metal transfer and degassing system
US9903383B2 (en) 2013-03-13 2018-02-27 Molten Metal Equipment Innovations, Llc Molten metal rotor with hardened top
US10052688B2 (en) 2013-03-15 2018-08-21 Molten Metal Equipment Innovations, Llc Transfer pump launder system
US10138892B2 (en) 2014-07-02 2018-11-27 Molten Metal Equipment Innovations, Llc Rotor and rotor shaft for molten metal
US10267314B2 (en) 2016-01-13 2019-04-23 Molten Metal Equipment Innovations, Llc Tensioned support shaft and other molten metal devices
US10428821B2 (en) 2009-08-07 2019-10-01 Molten Metal Equipment Innovations, Llc Quick submergence molten metal pump

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9108052U1 (en) * 1991-06-29 1991-08-14 Sigri Gmbh, 8901 Meitingen, De
DE4309267C1 (en) * 1993-03-23 1994-04-21 Karsten Tellert Oxidn. protection of ceramic esp. silicon carbide - using glaze-forming impregnation soln. contg. hydroxy:propionic and ethanoic acids

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685541A (en) * 1952-03-14 1954-08-03 Great Lakes Carbon Corp Refractory carbon and method of producing the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2482933A (en) * 1947-07-16 1949-09-27 Augustin L J Queneau Glass impregnated carbon articles
US2685539A (en) * 1951-12-21 1954-08-03 Great Lakes Carbon Corp Refractory carbon and method of producing the same
US2685540A (en) * 1952-03-14 1954-08-03 Great Lakes Carbon Corp Refractory carbon and method of producing the same
US2685542A (en) * 1953-04-07 1954-08-03 Great Lakes Carbon Corp Refractory carbon and method of producing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685541A (en) * 1952-03-14 1954-08-03 Great Lakes Carbon Corp Refractory carbon and method of producing the same

Cited By (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065088A (en) * 1959-09-30 1962-11-20 Union Carbide Corp Oxidation-resistant graphite article and method
US3342627A (en) * 1964-05-05 1967-09-19 Pure Carbon Company Inc Method for impregnating graphite bodies and the article produced therefrom
US3351477A (en) * 1966-01-27 1967-11-07 Union Carbide Corp Treat solution for rendering carbonaceous articles oxidation resistant
US3804648A (en) * 1970-12-11 1974-04-16 Ici Ltd Graphite compositions
US4617232A (en) * 1982-04-15 1986-10-14 Kennecott Corporation Corrosion and wear resistant graphite material
US4621017A (en) * 1982-04-15 1986-11-04 Kennecott Corporation Corrosion and wear resistant graphite material and method of manufacture
US4439491A (en) * 1982-11-18 1984-03-27 Great Lakes Carbon Corporation Oxidation retardant for graphite
US4530853A (en) * 1984-06-06 1985-07-23 Great Lakes Carbon Corporation Non-conducting oxidation retardant coating composition for carbon and graphite
US4726995A (en) * 1985-11-13 1988-02-23 Union Carbide Corporation Oxidation retarded graphite or carbon electrode and method for producing the electrode
US5401440A (en) * 1993-01-13 1995-03-28 The B. F. Goodrich Company Inhibition of catalyzed oxidation of carbon-carbon composites
US5759622A (en) * 1994-03-18 1998-06-02 The B.F. Goodrich Company Method of inhibiting catalyzed oxidation of carbon-carbon composites
US6551709B1 (en) 1994-03-18 2003-04-22 Goodrich Corporation Methods of inhibiting catalyzed oxidation of carbon-carbon composites using phosphoric acid, a zinc salt, and an aluminum salt and articles made therefrom
US8440135B2 (en) 2002-07-12 2013-05-14 Paul V. Cooper System for releasing gas into molten metal
US20090269191A1 (en) * 2002-07-12 2009-10-29 Cooper Paul V Gas transfer foot
US9435343B2 (en) 2002-07-12 2016-09-06 Molten Meal Equipment Innovations, LLC Gas-transfer foot
US8110141B2 (en) 2002-07-12 2012-02-07 Cooper Paul V Pump with rotating inlet
US8178037B2 (en) 2002-07-12 2012-05-15 Cooper Paul V System for releasing gas into molten metal
US9034244B2 (en) 2002-07-12 2015-05-19 Paul V. Cooper Gas-transfer foot
US8361379B2 (en) 2002-07-12 2013-01-29 Cooper Paul V Gas transfer foot
US8529828B2 (en) 2002-07-12 2013-09-10 Paul V. Cooper Molten metal pump components
US8409495B2 (en) 2002-07-12 2013-04-02 Paul V. Cooper Rotor with inlet perimeters
US8501084B2 (en) 2003-07-14 2013-08-06 Paul V. Cooper Support posts for molten metal pumps
US8075837B2 (en) 2003-07-14 2011-12-13 Cooper Paul V Pump with rotating inlet
US7906068B2 (en) 2003-07-14 2011-03-15 Cooper Paul V Support post system for molten metal pump
US8475708B2 (en) 2003-07-14 2013-07-02 Paul V. Cooper Support post clamps for molten metal pumps
US10458708B2 (en) 2007-06-21 2019-10-29 Molten Metal Equipment Innovations, Llc Transferring molten metal from one structure to another
US9643247B2 (en) 2007-06-21 2017-05-09 Molten Metal Equipment Innovations, Llc Molten metal transfer and degassing system
US9855600B2 (en) 2007-06-21 2018-01-02 Molten Metal Equipment Innovations, Llc Molten metal transfer system and rotor
US9925587B2 (en) 2007-06-21 2018-03-27 Molten Metal Equipment Innovations, Llc Method of transferring molten metal from a vessel
US8613884B2 (en) 2007-06-21 2013-12-24 Paul V. Cooper Launder transfer insert and system
US8366993B2 (en) 2007-06-21 2013-02-05 Cooper Paul V System and method for degassing molten metal
US8753563B2 (en) 2007-06-21 2014-06-17 Paul V. Cooper System and method for degassing molten metal
US9581388B2 (en) 2007-06-21 2017-02-28 Molten Metal Equipment Innovations, Llc Vessel transfer insert and system
US10352620B2 (en) 2007-06-21 2019-07-16 Molten Metal Equipment Innovations, Llc Transferring molten metal from one structure to another
US9017597B2 (en) 2007-06-21 2015-04-28 Paul V. Cooper Transferring molten metal using non-gravity assist launder
US9409232B2 (en) 2007-06-21 2016-08-09 Molten Metal Equipment Innovations, Llc Molten metal transfer vessel and method of construction
US9566645B2 (en) 2007-06-21 2017-02-14 Molten Metal Equipment Innovations, Llc Molten metal transfer system and rotor
US9862026B2 (en) 2007-06-21 2018-01-09 Molten Metal Equipment Innovations, Llc Method of forming transfer well
US9156087B2 (en) 2007-06-21 2015-10-13 Molten Metal Equipment Innovations, Llc Molten metal transfer system and rotor
US9205490B2 (en) 2007-06-21 2015-12-08 Molten Metal Equipment Innovations, Llc Transfer well system and method for making same
US8337746B2 (en) 2007-06-21 2012-12-25 Cooper Paul V Transferring molten metal from one structure to another
US9909808B2 (en) 2007-06-21 2018-03-06 Molten Metal Equipment Innovations, Llc System and method for degassing molten metal
US9982945B2 (en) 2007-06-21 2018-05-29 Molten Metal Equipment Innovations, Llc Molten metal transfer vessel and method of construction
US9383140B2 (en) 2007-06-21 2016-07-05 Molten Metal Equipment Innovations, Llc Transferring molten metal from one structure to another
US10072891B2 (en) 2007-06-21 2018-09-11 Molten Metal Equipment Innovations, Llc Transferring molten metal using non-gravity assist launder
US10274256B2 (en) 2007-06-21 2019-04-30 Molten Metal Equipment Innovations, Llc Vessel transfer systems and devices
US10345045B2 (en) 2007-06-21 2019-07-09 Molten Metal Equipment Innovations, Llc Vessel transfer insert and system
US10195664B2 (en) 2007-06-21 2019-02-05 Molten Metal Equipment Innovations, Llc Multi-stage impeller for molten metal
US9506129B2 (en) 2009-08-07 2016-11-29 Molten Metal Equipment Innovations, Llc Rotary degasser and rotor therefor
US9464636B2 (en) 2009-08-07 2016-10-11 Molten Metal Equipment Innovations, Llc Tension device graphite component used in molten metal
US9470239B2 (en) 2009-08-07 2016-10-18 Molten Metal Equipment Innovations, Llc Threaded tensioning device
US9382599B2 (en) 2009-08-07 2016-07-05 Molten Metal Equipment Innovations, Llc Rotary degasser and rotor therefor
US9377028B2 (en) 2009-08-07 2016-06-28 Molten Metal Equipment Innovations, Llc Tensioning device extending beyond component
US8449814B2 (en) 2009-08-07 2013-05-28 Paul V. Cooper Systems and methods for melting scrap metal
US9080577B2 (en) 2009-08-07 2015-07-14 Paul V. Cooper Shaft and post tensioning device
US10428821B2 (en) 2009-08-07 2019-10-01 Molten Metal Equipment Innovations, Llc Quick submergence molten metal pump
US8535603B2 (en) 2009-08-07 2013-09-17 Paul V. Cooper Rotary degasser and rotor therefor
US8524146B2 (en) 2009-08-07 2013-09-03 Paul V. Cooper Rotary degassers and components therefor
US9657578B2 (en) 2009-08-07 2017-05-23 Molten Metal Equipment Innovations, Llc Rotary degassers and components therefor
US8444911B2 (en) 2009-08-07 2013-05-21 Paul V. Cooper Shaft and post tensioning device
US9422942B2 (en) 2009-08-07 2016-08-23 Molten Metal Equipment Innovations, Llc Tension device with internal passage
US9328615B2 (en) 2009-08-07 2016-05-03 Molten Metal Equipment Innovations, Llc Rotary degassers and components therefor
US8714914B2 (en) 2009-09-08 2014-05-06 Paul V. Cooper Molten metal pump filter
US9108244B2 (en) 2009-09-09 2015-08-18 Paul V. Cooper Immersion heater for molten metal
US10309725B2 (en) 2009-09-09 2019-06-04 Molten Metal Equipment Innovations, Llc Immersion heater for molten metal
US9482469B2 (en) 2010-05-12 2016-11-01 Molten Metal Equipment Innovations, Llc Vessel transfer insert and system
US9410744B2 (en) 2010-05-12 2016-08-09 Molten Metal Equipment Innovations, Llc Vessel transfer insert and system
US9497804B2 (en) 2010-07-01 2016-11-15 Graftech International Holdings Inc. Graphite electrode
US9253827B2 (en) 2010-07-01 2016-02-02 Graftech International Holdings, Inc. Graphite electrodes
US8923360B2 (en) 2010-07-01 2014-12-30 Graftech International Holdings Inc. Graphite electrodes
US9903383B2 (en) 2013-03-13 2018-02-27 Molten Metal Equipment Innovations, Llc Molten metal rotor with hardened top
US10126059B2 (en) 2013-03-14 2018-11-13 Molten Metal Equipment Innovations, Llc Controlled molten metal flow from transfer vessel
US10126058B2 (en) 2013-03-14 2018-11-13 Molten Metal Equipment Innovations, Llc Molten metal transferring vessel
US10302361B2 (en) 2013-03-14 2019-05-28 Molten Metal Equipment Innovations, Llc Transfer vessel for molten metal pumping device
US9587883B2 (en) 2013-03-14 2017-03-07 Molten Metal Equipment Innovations, Llc Ladle with transfer conduit
US9011761B2 (en) 2013-03-14 2015-04-21 Paul V. Cooper Ladle with transfer conduit
US10052688B2 (en) 2013-03-15 2018-08-21 Molten Metal Equipment Innovations, Llc Transfer pump launder system
US10307821B2 (en) 2013-03-15 2019-06-04 Molten Metal Equipment Innovations, Llc Transfer pump launder system
US10322451B2 (en) 2013-03-15 2019-06-18 Molten Metal Equipment Innovations, Llc Transfer pump launder system
US10465688B2 (en) 2014-07-02 2019-11-05 Molten Metal Equipment Innovations, Llc Coupling and rotor shaft for molten metal devices
US10138892B2 (en) 2014-07-02 2018-11-27 Molten Metal Equipment Innovations, Llc Rotor and rotor shaft for molten metal
US10267314B2 (en) 2016-01-13 2019-04-23 Molten Metal Equipment Innovations, Llc Tensioned support shaft and other molten metal devices

Also Published As

Publication number Publication date
DE1131586B (en) 1962-06-14

Similar Documents

Publication Publication Date Title
Groves et al. Solid solution and precipitation hardening in Mg‐Fe‐O alloys
US3551101A (en) Preparation of sintered aluminum nitride
US4425407A (en) CVD SiC pretreatment for carbon-carbon composites
US4312954A (en) Sintered silicon carbide ceramic body
US20030138673A1 (en) High temperature amorphous composition based on aluminum phosphate
US3342627A (en) Method for impregnating graphite bodies and the article produced therefrom
US3174895A (en) Graphite cloth laminates
US1107011A (en) Method of bonding fused crystalline alumina.
US3881039A (en) Process for the treatment of amorphous carbon or graphite manufactured articles, for the purpose of improving their resistance to oxidation, solutions suitable for attaining such purpose and resulting product
EP0170817A2 (en) A high-purity powder of hexagonal boron nitride and a method for the preparation thereof
US4439491A (en) Oxidation retardant for graphite
US3574548A (en) Process for manufacturing a cellular carbon body
Freeman et al. The application of the absolute rate theory to the ignition of propagatively reacting systems. The thermal ignition of the systems lithium nitrate–magnesium, sodium nitrate–magnesium
US4895713A (en) Intercalation of graphite
US3903230A (en) Method for producing ceramics of silicon nitride
US4725344A (en) Method of making electroluminescent phosphor films
US3860443A (en) Graphite composite
RU2084425C1 (en) Method of manufacturing articles from carbon-silicon carbide composite material and carbon-silicon carbide composite material
US2938807A (en) Method of making refractory bodies
TW340106B (en) Process for producing microporous ceramics
US4320204A (en) Sintered high density boron carbide
US3923675A (en) Method for preparing lead lanthanum zirconate-titanate powders
GB2309457A (en) Melamine borate
EP0134254B1 (en) Method of making silicon-infiltrated reaction-bonded silicom carbide bodies
US2270199A (en) Graphite article