US3210202A - Molding sand - Google Patents

Molding sand Download PDF

Info

Publication number
US3210202A
US3210202A US213094A US21309462A US3210202A US 3210202 A US3210202 A US 3210202A US 213094 A US213094 A US 213094A US 21309462 A US21309462 A US 21309462A US 3210202 A US3210202 A US 3210202A
Authority
US
United States
Prior art keywords
humate
organophilic
alkyl
sand
alkyl ammonium
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
US213094A
Other languages
English (en)
Inventor
Jack C Cowan
Hugh G Gainey
Iii Harvey M Oyler
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.)
NL Industries Inc
Original Assignee
Nat Lead Co
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
Priority to BE635513D priority Critical patent/BE635513A/xx
Priority to NL295934D priority patent/NL295934A/xx
Application filed by Nat Lead Co filed Critical Nat Lead Co
Priority to US213094A priority patent/US3210202A/en
Priority to FR942675A priority patent/FR1381292A/fr
Priority to CH929563A priority patent/CH445032A/de
Priority to DEN23542A priority patent/DE1237265B/de
Application granted granted Critical
Publication of US3210202A publication Critical patent/US3210202A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/1305—Organic additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/167—Mixtures of inorganic and organic binding agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients

Definitions

  • This invention relates to molding sands such as are used for the casting of metals, and more particularly to an improvement in molding sands of the type which are bonded with materials other than ordinary clay as such and liquids other than water.
  • a molten metal is poured into a mold formed from a suitable comminuted temperature-resistant mineral, commonly known as sand, and indeed generally consisting of quartz sand, which is bonded by the use of a relatively minor amount of suitable bonding agent, which most commonly has been clay tempered with some water.
  • Non-aqueous systems of this type are described, for example, in Canadian Patent 572,142 and U.S. Patent 3,027,265. Even such systems fall short of perfection, however, and the present invention is concerned with improvements in essentially non-aqueous molding sand compositions of this general type.
  • An object of the present invention is to provide a molding sand containing a completely organic bonding agent which is effective in a non-aqueous lubricant vehicle.
  • Another object of the invention is to provide a molding sand containing such an organic bonding agent together with an organophilic clay, likewise with the employment of a non-aqueous lubricant.
  • a molding sand mix a foundry sand; and a binder which consists of a mixture of a suitable organic liquid as hereinafter described in greater detail, but which may be for example diesel oil, together with a long chain alkyl ammonium humate and which may be conjoined with an organophilic clay in any proportion from zero to four parts of the organophilic clay for each part of the long chain alkyl ammonium humate.
  • a suitable organic liquid as hereinafter described in greater detail, but which may be for example diesel oil, together with a long chain alkyl ammonium humate and which may be conjoined with an organophilic clay in any proportion from zero to four parts of the organophilic clay for each part of the long chain alkyl ammonium humate.
  • other additives common in the non-aqueous molding sand art may also be present, such as for example silica flour, finely divided iron oxide, and the like.
  • the organic liquid need not be a single chemical species but may be
  • the alkyl ammonium humate is fundamentally an onium salt of humic acid.
  • the humic acid is most readily and economically obtained from lignite, the alkalisoluble portion of which may be considered to be humic acid for the purpose of this invention, and indeed that is the case from a chemical standpoint.
  • Humic acid is a material of Wide distribution, being present in soils, peat, and coals, especially coals of the type known as lignite or brown coal. Although the exact details of its chemical structure are not completely known, it is a surprisingly uniform substance considering the variety of source materials of which it represents a natural product of degradation, such as leaves, wood, and the like vegetable organic matter. It is an acid, in which both carboxyl and phenolic hydroxyl groups contribute basecombining ability. It is soluble in alkalies, such as caustic soda and sodium carbonate, has a deep brown color, and is readily soluble in water when converted to its alkali metal salt, which may be then termed an alkali metal humate, the commonest example of which is sodium humate.
  • humic acid is present in soils and peat, and may readily be extracted from these by known means, most commonly by treatment with dilute aqueous alkali.
  • humic acid is nearly always derived from its richest common source, which is lignite, of which there are vast deposits distributed throughout the world, including the United States, and particularly the states of North Dakota, Texas, New Mexico, and California.
  • the alkyl ammonium humate used in the practice of our invention may be more particularly described as a salt of humic acid, viz., a humate, in which the cation is a substituted ammonium ion, in which one or more of the hydrogen atoms originally present in the ammonium ion is substituted by an alkyl radical, including substituted ammonium cations in which two or more of the substituted positions may form part of a ring (as in the case of imidazolinium), and in which at least one of the said alkyl radicals has from 14 to 22 carbon atoms in a straight chain.
  • a humate in which the cation is a substituted ammonium ion, in which one or more of the hydrogen atoms originally present in the ammonium ion is substituted by an alkyl radical, including substituted ammonium cations in which two or more of the substituted positions may form part of a ring (as in the case of imidazolini
  • the valence positions of the nitrogen atom which are not occupied by hydrogen atoms may be either long alkyl chains, of the type just described, or may be short alkyl chains, from C to C that is, methyl through tridecyl, or phenyl or benzyl radicals, as long as at least one alkyl radical is present in the range of at least C to C which in the methane series corresponds to tetradecyl through docosyl.
  • the term includes substituted ammonium cations in which two or more of the substituted positions may form part of a ring, as is the case in the imidazolinium compounds listed above. It will be further understood that the above listing is illustrative and by no means exhaustive.
  • the alkyl ammonium humate compounds to be used in our invention may be produced by bringing together humic acid and the alkyl ammonium compound in its base form.
  • the base and the acid neutralize each other with salt formation, so as to produce an alkyl ammonium humate in accordance with the invention.
  • Another general method of preparation is to convert the humic acid to a simple salt by reaction with an alkali, so as to produce sodium humate, potassium humate, ammonium humate, and the like, by reaction with sodium hydroxide, potassium hydroxide, or ammonium hydroxide, respectively.
  • the alkyl ammonium compound is caused to be present in the form of a simple salt.
  • a primary, secondary, or tertiary amine may be reacted with a simple acid such as hydrochloric, acetic, and the like to give the corresponding substituted ammonium chloride or acetate, respectively.
  • a simple acid such as hydrochloric, acetic, and the like
  • This method of procedure has the advantage that the simple substituted ammonium salts, and the simple humates as described, are both water soluble, so that solutions of each reactant may be made, and the reaction completed by mixing the solutions together.
  • octadecyl amine is treated with an equivalent quantity of acetic acid to give octadecylammonium acetate. This is then dissolved in several times its weight in water.
  • humic acid is converted to sodium humate by treating lignite, for example, with sodium hydroxide to neutrality followed by filtering off the insoluble portion of the lignite.
  • the solution of sodium humate thus formed is mixed with the solution of octadecylammonium acetate in stoichiometrically equivalent proportions, whereupon there occurs a quantitative precipitation of octadecylammonium humate.
  • the equivalent weight of the humic acid can readily be determined in any known fashion applicable to acids generally, such as, for example, by titration of sodium hydroxide using an electrometric pH meter.
  • a somewhat special case is presented by the quaternary substituted ammonium salts, which have no free base form.
  • a simple example is trimethyl octadecylammonium chloride.
  • an alkali humate such as sodium humate
  • it may also be reacted directly with humic acid, although the reaction is accelerated by adding some base such as sodium hydroxide to the reaction mixture to neutralize the acid which is formed as a result of the reaction, which in the particular example considered here would be hydrochloric acid.
  • the quaternary ammonium compounds may be in their hydroxide form, of course, and may then be reacted directly with humic acid.
  • the organophilic clay is chosen from the group which consists of organophilic montmorillonite and organophilic attapulgite and indeed mixtures thereof in any proportion. Such organophilic clays are now a well known article of commerce, and are described in extensive technical and patent literature.
  • organophilic clays are made by starting with a clay of substantial base exchange capacity, the most commonly used of which are montmorillonite as represented, for example, by Wyoming bentonite or by hectorite, and attapulgite, and etfecting a cation exchange by replacing the bases present in the clay, which may be for example, sodium, calcium, hydrogen and the like, with a long chain onium cation, which indeed is most often a long chain alkyl ammonium ion, and may be chosen from the same class already described hereinabove in connection with the alkyl ammonium humate.
  • a clay of substantial base exchange capacity the most commonly used of which are montmorillonite as represented, for example, by Wyoming bentonite or by hectorite, and attapulgite
  • a cation exchange by replacing the bases present in the clay, which may be for example, sodium, calcium, hydrogen and the like
  • a long chain onium cation which indeed is most often a long chain alkyl
  • Organophilic clays are described in Hauser Patent 2,531,427; Jordan Patent 2,531,440; Miericke Patent 3,027,265; and Canadian Patent 572,142; and indeed many others. They are also described in the book Clay Mineralogy by Ralph E. Grim, New York, 1953, pages 265-269; and in the book entitled The Colloid Chemistry of Silica and Silicates by Ralph K. Iler, Ithaca, 1955, pages 225226. Organophilic clays are commercially available under the trademark Bentone. In general, the organophilic clays commercially available and useful in our invention have within narrow limits the exact amount of long chain onium ion reacted with the clay which corresponds to the cation exchange capacity of the latter. Organophilic clays are generally produced and are commercially available in the form of a fine, dry powder, generally about 200 mesh.
  • the organic liquid which is used together with the alkyl ammonium humate and, when present, with the organophilic clay in order to form a binder or bonding agent for the sand so as to make it into a moldable composition may be selected from a very large group of organic liquids indeed.
  • Suitable organic liquids, which incidentally meet the criterion of molecular weight just stated, are normal octyl alcohol; tall oil; nonyl phenol; various aromatic and paraflinic oils such as diesel oil, fuel oil,
  • coal tar oil and the like; the polyethylene glycols commercially available, for example, under the trademark Carbowax and having average molecular weights from about 200 to about 400; the analogous polypropylene glycols which again have molecular weights from about to about 1,000; phosphate esters of ethoxylated alkyl phenols which are commercially available and are described in Chemical and Engineering News, December 25, 1961, page 40; and the like. Mixtures of these various liquids are also quite useful. Examples of the latter are mixtures in various proportions of diesel oil and octyl alcohol; and diesel oil and the phosphate esters just described.
  • Example 1 Dimethyl-di(hydrogenated tallow) ammonium humate was prepared by mixing together 120.5 parts by weight of North Dakota lignite, of the weathered, alkali-soluble variety described in US. Bur. Mines R.I., 5611, with 22.5 parts water, 16 parts caustic soda, and 44 parts of a commercial dimethyl-di(hydrogenated tallow) ammonium chloride. 200 parts of diesel oil were then added and the entire mixture subjected to high speed agitation for ten minutes. A homogeneous concentrate resulted.
  • Example 2 Dimethyl-di(hydrogenated tallow) ammonium humate was prepared by mixing together 100 parts by weight of the same lignite as described in Example 1 with 36 parts of a commercial sodium tetraborate decahydrate, and 1000 parts of water. The borax served as an alkalizer to form sodium humate. This mixture was stirred and heated at 170 F. for 45 minutes. 100 parts of a commercial dimethyl-di(hydrogenated tallow) ammonium chloride was then added to the hot mixture and the resulting precipitate was filtered, dried, and ground.
  • Dimethyl-di(hydrogenated tallow) ammonium montmorillonite was prepared by mixing 90 milliequivalents of a commercial dimethyl-di(hydrogenated tallow) am monium chloride per 100 grams of commercial Wyoming bentonite with enough water to give a consistency appropriate for pugging the mixture, which was about 30 grams of water. A conventional pug mill was used. The resulting extrusions were dried and ground.
  • a molding sand composition comprising as essential ingredients sand, and a binder consisting essentially of alkyl ammonium humate, said alkyl having from 14 to 22 carbon atoms in a straight chain, together with from zero to four parts of organophilic clay chosen from the group which consists of organophilic montmorillonite and organophilic attapulgite and mixtures thereof for each part of said alkyl ammonium humate, and an organic liquid having a molecular weight of at least 125 in an amount within the range of 1/10 to 1 /2 part for each part of said alkyl ammonium humate plus said organophilic clay, said molding sand having a green compressive strength of at least 2.4 pounds per square inch.
  • a molding sand composition comprising as essential ingredients sand, and from about 1 to about 10 parts per parts of said sand of a binder consisting essentially of alkyl ammonium humate, said alkyl having from 14 to 22 carbon atoms in a straight chain, together with from zero to four parts of organophilic clay chosen from the group which consists of organophilic montmorillonite and organophilic attapulgite and mixtures thereof for each part of said alkyl ammonium humate, and an organic liquid having a molecular weight of at least in an amount within the range of 1/ 10 to 1 /2 part for each part of said alkyl ammonium humate plus said organophilic clay, said molding sand having a green compressive strength of at least 2.4 pounds per square inch.
  • a molding sand composition comprising as essential constituents sand, and a binder consisting essentially of alkyl ammonium humate, said alkyl having from 14 to 22 carbon atoms in a straight chain, together with from zero to four parts of organophilic montmorillonite and organophilic attapulgite and mixtures thereof for each part of said alkyl ammonium humate, and an organic liquid having a molecular weight of at least 125 in an amount suflicient to impart to said molding sand a green compressive strength of at least 2.4 pounds per square inch.
  • a molding sand composition comprising as essential constituents sand, and a binder consisting essentially of alkyl ammonium humate, said alkyl having from 14 to 22 carbon atoms in a straight chain, together with from Zero to four parts of organophilic montmorillonite and organophilic attapnlgite and mixtures thereof for each part of said alkyl ammonium humate, and an organic liquid of a kind and in an amount sufllcient to impart to said molding sand a green compressive strength of at least 2.4 pounds per square inch.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
US213094A 1962-07-30 1962-07-30 Molding sand Expired - Lifetime US3210202A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE635513D BE635513A (en:Method) 1962-07-30
NL295934D NL295934A (en:Method) 1962-07-30
US213094A US3210202A (en) 1962-07-30 1962-07-30 Molding sand
FR942675A FR1381292A (fr) 1962-07-30 1963-07-25 Sable de moulage
CH929563A CH445032A (de) 1962-07-30 1963-07-25 Formsandmischung
DEN23542A DE1237265B (de) 1962-07-30 1963-07-30 Formsand-Bindemittel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US213094A US3210202A (en) 1962-07-30 1962-07-30 Molding sand

Publications (1)

Publication Number Publication Date
US3210202A true US3210202A (en) 1965-10-05

Family

ID=22793710

Family Applications (1)

Application Number Title Priority Date Filing Date
US213094A Expired - Lifetime US3210202A (en) 1962-07-30 1962-07-30 Molding sand

Country Status (5)

Country Link
US (1) US3210202A (en:Method)
BE (1) BE635513A (en:Method)
CH (1) CH445032A (en:Method)
DE (1) DE1237265B (en:Method)
NL (1) NL295934A (en:Method)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1558130B1 (de) * 1966-04-13 1974-01-24 Nl Industries Inc Formsandmasse, die aus sand, wasser, einem in wasser hochquellenden bentonit und einem wasserloeslichen alkalisalz besteht

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1558130B1 (de) * 1966-04-13 1974-01-24 Nl Industries Inc Formsandmasse, die aus sand, wasser, einem in wasser hochquellenden bentonit und einem wasserloeslichen alkalisalz besteht

Also Published As

Publication number Publication date
NL295934A (en:Method)
CH445032A (de) 1967-10-15
BE635513A (en:Method)
DE1237265B (de) 1967-03-23

Similar Documents

Publication Publication Date Title
CA1285746C (en) Organophilic polyphenolic acid adducts
DE3135892C2 (de) Als Verdickungsmittel verwendbare nichtwäßrige Aufschlämmungen
US4469639A (en) Preparation of organically modified smectites by treatment with methyl benzyl dialkyl ammonium halide
US4359339A (en) Bentonite clay and water soluble aluminum salt compositions
DE99950921T1 (de) Fliessfähige, wässrige borhaltige zusammensetzungen und verfahren zu ihrer herstellung
DE2022347A1 (de) Durch organisches Amin und starke Base stabilisierte Kieselsaeuresole mit hoher Oberflaeche
US4422855A (en) Method of thickening solutions using normally nongelling clays
US3210202A (en) Molding sand
US3775447A (en) Lignite products and compositions thereof
DE2951171A1 (de) Verfahren zur bildung von agglomeraten aus kohle und oel
US5248641A (en) Process for producing bentonite clays exhibiting enhanced solution viscosity properties
US3210203A (en) Molding sand
US2133759A (en) Compositions for and process of making suspensions
US2128404A (en) Composition
GB1468744A (en) Process for the preparation of foundry moulding sand
DE69432039T2 (de) Mit organischen Verbindungen modifizierte Tone als Additive für hochviskose Systeme
US1795011A (en) Molding sand and process of using
US3403037A (en) Foundry core and molding sand composition
US3325537A (en) Process of solubilizing lignite and producing humates
US3014871A (en) New compounds and lubricant compositions containing same
US2237593A (en) Foundry composition and method
WO1992005123A1 (en) Process for producing bentonite clays exhibiting enhanced solution viscosity properties
JPH0662290B2 (ja) 膨潤性ケイ酸塩の製造方法
US3290243A (en) Bodying organic liquids with colloidal clay and clay composition therefor
JPS6042451A (ja) 有機クレ−の乾式製造法