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M. 19

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ILLINOIS STATE GEOLOGICAL SURVEY

JohnC. Frye, Chief Urbana, IllinoisNovember, 1964

NDUSTRIAL MINERALS NOTES • No. 19

BINDING MATERIALS USED IN

MAKING PELLETS AND BRIQUETS

G. R. YOHE

ABSTRACT

This compilation of information about materials that have been usedas binders in making pellets, briquets, or other products shaped from powderedor granular substances was prepared for use in the Illinois State GeologicalSurvey laboratories. Although it is not an exhaustive report, other workersalso may find it useful.

Information from about 200 abstracts selected from Chemical Abstractsfor 1937 through 1963 is Included. Both organic and inorganic binding materialsare discussed.

The original reference and the Chemical Abstracts citation are givenin the list of references. The report is indexed.

In connection with work in progress at the Illinois State GeologicalSurvey, a need arose for a compilation of information about materials that hadfound application as binders in the making of pellets, briquets, or otherarticles formed from powdered or granular material.

Although this report is by no means exhaustive, it may be of interestand value to workers in other laboratories. The decision was therefore madeto distribute it as an Industrial Minerals Note.

According to Webster's New International Dictionary (2nd edition),a binder is "anything that causes cohesion in loosely assembled substances!as tar, asphalt, or crushed stone in a road."

This definition is somewhat too broad for the present discussion,for it would include such things as water (which serves as a temporary binderfor sand as children build their castles at the beach) or mucilage with whichwe fasten a postage stamp to an envelope. In the broad sense, anything thatserves as an adhesive might be called a binder.

This discussion is restricted to substances that can be mixed withpowdered or granular solids for the purpose of forming pellets or briquetshaving reasonably good resistance to weathering and a fair degree of stabilityin handling. Even with this limitation, it is scarcely possible to assemblecomplete information, as there are many kinds of materials to be bound, manypotential binders, and many purposes for using binders.

Indexes to Chemical Abstract s for 1957 through 1963 were used, butonly selected references were examined. For example, under "Binders" onlythose entries deemed pertinent were looked up, and under headings' that referto materials being bonded, "binders for" references were selected. Numeroustopics, including adhesives, cements, fibers, inks, lacquers, lime, mortar,paints, plaster, resins, and rubbers were excluded.

In this review, binders are divided into two categories, inorganicand organic. Under each of these headings, the various binding materials arelisted in alphabetical order. This is not completely satisfactory, as manymixtures have been described, some comprising inorganic, some organic, andsome both inorganic and organic materials. However, this arrangement is con-sidered preferable to one in which the key words are derived from the materialsbeing bonded, as many binders have been described without reference to thekinds of materials with which they may suitably be used. The index lists

binders, materials bonded, and other items such as additives and solvents.

The forces that enable materials to serve as binders are not all

of the same nature. Most organic binders function essentially as "glues" or

sticky types of adhesive that' wet the surfaces of the particles being bondedand thus cement them together. Some such binders are applied as hot liquids

and become solid when cool, and others may remain in a more or less viscous

liquid state. Some inorganic binders (fusible metals, for example) also

function in this manner.

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Other binders are solids of very small particle size. Becauseof their high surface energy these particles adhere firmly to other sur-

faces, and thus may serve as bonding agents between neighboring particlesof the material being bonded. Most binders that function in this mannerare inorganic materials; clays, colloidal alumina, and colloidal silicaare examples.

Some binding action may involve both of these principles. Anore pellet might possess sufficient "green" or "dry" strength because ofsurface energy forces, and then be permanently bonded by being heated toa partial fusion stage wherein forces of the first described type comeinto play.

Acknowledgment . The assistance of Mr. Touradj Adl in search-ing Chemical Abstracts is gratefully acknowledged.

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INORGANIC BINDERS

ALUMINA

A U. S. patent issued in 1961 to John Bugosh and assigned to thedu Pont Company* describes the preparation and use of fibrous boehmite, a

hydrated alumina (A100H). This material, which can carry a positive charge,is used to coat surfaces (e.g., glass, paper) that have been given a negativecharge. The coating can then serve to anchor a top coat of other desiredmaterial by virtue of its OH groups, its electrical charge, or its fibrousphysical nature.

Another publication issued by the du Pont Company2 describes the

binding action of this same material (but calls it "Baymal Colloidal Alumina")and indicates that the boehmite fibrils are approximately 50 angstrom units indiameter and several hundred angstroms long. If an aqueous suspension of thesefibrils is applied to a material such as asbestos that is made up of largerfibers or to one composed of spherical or granular particles, the evaporationof water leaves a gel first and then a mat or "felt" of the boehmite fibrils.

At points of contact of the fibers or particles, this mat bonds the materialtogether.

ALUMINATES

A Hungarian patent3 describes the use of alkali aluminates, or

aluminates of Zn, Sn, Sb, and Cr which do not contain much free alkali, mixed

in a ratio of 1.7:6.0 with neutral or almost neutral solutions of alkali sili-

cates or alkali fluosilicates. After the product is pressed or centrifuged and

dried below 100° C, it is subjected to a hydrolytic treatment with water prior

to use.

ALUMINUM

Aluminum nitride (A1N), which is useful as a refractory material for

contact with liquid or gaseous aluminum, has such a high sintering temperature

that common binders are not suitable for bonding it.

A French patent4 describes the use of powdered metallic aluminum,

which is added to the A1N powder with gum arable, sodium silicate, or ceresin

prior to shaping and compressing the pieces. A mixture containing 20, 15, 1,

and 58 percent of 25 to 50, 50 to 100, 100 to 200, and -200 mesh aluminum,

respectively, is recommended.

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ALUMINUM PHOSPHATE AND PHOSPHORIC ACID

Making castable refractories by bonding alumina, zirconia, mullite,beryllium oxide, or silicon carbide with phosphoric acid or aluminum phosphatehas been described. 5 A complex amine was used as an inhibitor, and the addi-tion of ammonium fluoride accelerated the setting of the refractory.

ANHYDRITE (See Calcium Sulfate.)

ATTAPULGITE

Zoelitic molecular sieves, described in a German patent, 6 were madeby mixing zeolites with 1 to 40 percent of attapulgite (a hydrous magnesiumaluminum silicate characterized by a distinctive rodlike particle shape) andwaher, drying the mixture for two hours at 90° C, and firing the shaped arti-cles at 650° C.

BORATE GLASSES

In the manufacture of abrasive discs, 7 borate glass has been usedas a bonding material. The mechanical properties of the abrasives dependupon the percentage of a colorless, needlelike mineral at the contact of thecorundum grains with the bond.

8 The amount of this mineral varied with theamount of B2O3 in the bond, and its composition was 3Al203«B203 .

A French patent9 describes the use of alkali metal borosilicatesthat soften below 1100° C, together with a plastic clay to improve moldingqualities, for forming articles from oxides of Al, Zr, and Ti, from diamond,and from carbides of Si, B, U, and Ta. After being molded, the objects areheated to about 1100° C.

CALCIUM CHR0MITES

Calcium chromites, prepared by heating mixtures of CaO and Cr203in the presence of air, have been shown to possess hydraulic binding proper-ties.

10

CALCIUM FLUORIDE

Fluorspar (CaFg) has been used as a binder in making abrasive arti-cles and high-temperature bricks. 195

CALCIUM GERMANATE

,0Heating a mixture of 2CaO and Ge02 for three hours at 1250 C formsCa2Ge04 (calcium orthogermanate ) , which has "a significant degree of mechan-ical strength, and may be used as a binder. nl1

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CALCIUM OXIDE

Abrasives containing Si02 and A12 3 with the addition of trass (alight-colored volcanic tuff occurring especially along the lover Rhine) havebeen formed with calcium oxide as the binding agent. 12

CALCIUM AND SODIUM ALUMINATES

A U. S. patent13 describes the use of mixtures of calcium aluminateand sodium aluminate for bonding firebrick and refractory aggregates of fusedsilica, alumina, and kaolin. Such mixtures also bond insulating materials con-taining asbestos, diatomaceous earth, vermiculite, insulating firebrick, andgraphite. The amounts of the mixture of calcium aluminate and sodium aluminateused vary from 10 to 60 percent, and the unfired strength of the objects isbetter than when calcium aluminate alone is used.

CALCIUM SULFATE

A study of the reactions of anhydrite (calcium sulfate) when used asa binder for building materials has been published. 14

CEMENT P* JS CLAY

A French patent15 describes the admixture of clay with such bindersas cement in making shaped articles for which mechanical resistance is rela-tively unimportant. The clay, which should have a grain size below that of thebinder and should contain at least 15 percent AI2O3 and 40 percent Si02 , maycompose up to 50 percent of the weight of the mixture.

CHROMIUM COMPOUNDS

A U. S. patent 16 refers to the use of chromium ore or chromium com-

pounds as binders for dead-burned magnesite, but is concerned primarily with

the use of alkali metal tartrates for improving the quality and strength of

such materials. (See Tartrates under Organic Binders.)

CLAY

The effect of clay binders on the oxidation of sintered silicon car-

bide objects has been compared with the effect of silica gel. The clay binder

failed to prevent oxidation below 12^0° C. 17

Clay minerals or gels of Al(0H) 3 have been used to make abrasion-

resistant microspherical molecular sieve catalysts from synthetic zeolites. 18

A German patent19 describes the pelletizing of fine ores with a bind-

ing mixture consisting of clay and chalk with aqueous ferrous sulfate, starch,

and aqueous sodium hydroxide.

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FULLER'S EARTH

Fuller's earth ("florigel") kneaded with water to form a sticky,plastic mass has been used as a binder for catalysts and absorbents used inthe petroleum industry.

GLASS PLUS METAL

The binding of diamond abrasives by a mixture composed of a specialglass (softening point 2000° to 2350° F) and a metallic portion containingtungsten carbide, iron carbonyl, copper, and small amounts of manganese andgraphite is described in a U. S. patent. 21

IRON HUMATE

According to a Japanese patent, 22 a binder for fuel briquets is

prepared by extracting humic acids from peat or coalite with aqueous sodiumcarbonate and treating the extract with ferrous acetate to get a mixture con-taining iron humate.

IRON OXIDE PLUS CALCIUM OXIDE

The use of 4:1 to 2:1 mixtures of FeO and CaO in the manufacture ofhigh-silica refractories ("Dinas")23 from crystalline quartzites producesbricks of better and more uniform quality and higher compressive strength thanthese made with lower proportions of iron oxide in the binder.

LIME

The production of fine-grained lime from coarse limestone by a pro-

^si

patent.'cess of simultaneous heating and tumbling has been described in a German

24

The use of a mixture of calcium oxide and gypsum as a binder hasbeen demonstrated. 25

MAGNESIUM CHLORIDE

In the use of dolomite for hearth lining in a 5-ton basic electricfurnace, magnesium chloride was found to be a better binder than either sodiumsilicate or tar. 26

MAGNESIUM OXIDE

The preparation of magnesium oxide by precipitating with lime waterand subsequent calcining at 300° to 400° C is described in a Russian patent.27

Magnesium oxide prepared by firing magnesite has about twice thestrength of that from firing dolomite, and the strength is greater when the

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magnesite is fired at lower temperatures (65O to 700° c) than at higher andwhen fired short rather than long times. 28

A U. S. patent29 describes the manufacture of a refractory bond-forming material for nonacid refractory aggregates by firing a mixture offinely divided MgO and Si02 (20 to 60 percent of the latter) for half anhour at 1100° C.

MAGNESIUM SULFATE

The change in form that occurs when a dehydrated inorganic salt isconverted to the hydrated crystal form is the basis for the recommendation thata partially dehydrated magnesium sulfate be used industrially as a bindingmaterial. Setting begins in 3 minutes and is complete in 6 minutes. 30

METALS

A U. S. patent31 describes the forming of objects from powderedgraphite that had been mixed with a diffusionable binder, such as Zr, Nb,Mo, Ti, Cr, Si, or compounds of these which decompose to form the metals.For example, graphite containing k percent ZrH4 was pressed in a die at 1)000

lb/sq in.while being heated to l600° C in a reducing atmosphere and gave astrong, compact object of low porosity.

Titanium carbide articles have been formed with fusible metals as

binders. 32 Chromium and silicon adhered to TiC after cooling below the meltingpoint, but nickel and cobalt surrounded the TiC particles more thoroughly.Other metals tried were Al, Be, Nb, Au, Fe, Pb, Mg, Mn, Pt, Ti, and W.

The use of low-melting metals or alloys to bond powdered magneticmetals, such as alnico, has been patented in the United States. 33 The mixture

of powder, fusible metal (melting point belox^ i+50° c), and ZnCl2 as a flux is

heated to coat the alnico grains, then pressed into a mold at a temperature

above the melting point of the binder, and cooled.

METAL CARBIDES

A U. S. patent 34 describes the carbide-bonding of graphite articles.

A thermosetting synthetic resin is first used to bind the graphite particles

into the desired shape. After the resin is cured, the object is heated in a

neutral or reducing atmosphere in the presence of carbide-forming elements

(Hf, Zr, Ti, V, Ta, Cr, Mo, W, Th, U, B, or Si, or a mixture thereof) to enable

the elements to penetrate the object and react to form carbides in situ.

METAL CARBONYLS

This process, the subject of a Russian patent, 35 involves bonding

metal carbide or nitride powders by treating them with solutions of the carbon-

yls of the same metals, so that decomposition, presumably at an elevated temper-

ature, results in deposition of the metal that serves as the actual binder.

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METAL PLUS GLASS

A French patent36 describes the agglomeration of diamond powder witha mixture of 80 percent fine metal powder (85 percent Cu, 10 percent Sn, 5

percent Ag) and 20 percent fine glass (72 percent Si02 , 11 percent Na20, 5percent AI2O3, and 12 percent B2O3). The mixture is fritted in a reducingatmosphere at 700° to 76O C under pressure of 1 to 4 tons/sq cm.

PE0SPH0R0NITRILE DICHLORIDE POLYMERS

According to a German patent, 37 polymeric phosphoronitrile dichlo-ride (PNCl2 )n is used as a hinder for abrasives forming abrasive wheels. It

is prepared by refluxing 5.3 g NH4C1 and 20.8 g PC15 in 100 cc C2H2C14 , filter-ing when evolution of HC1 has ceased, recrystallizing the product from C2H4C12 ,

and heating it to 36°G. A water-soluble resin was made by heating 11 g hydro-quinone, 11 g resorcinol, and 18.6 g H3BO3 to 280° C. Thirty-eight grams ofthis powdered resin, 2 g of hexamethylenetetramine, and 8 g of (PNCl2 )n weremixed with carborundum and formed into a wheel at 175° C.

PHOSPHORUS ACIDS PLUS METAL OXIDES

Equal parts of H3PO4 and H2P2 7 were mixed with a dry metallic oxide(MgO and Fe3 4 are not suitable, but most others are) in a ratio of 1:3 to 3:1and heated 5 to 60 minutes at 250° to 400° F; then 2 to 5 percent of a dustingpowder such as MgO or MgC03 was added and the mixture ground to the desiredsize. This material, described in a U. S. patent, 38 can be used as a binderor as a molding composition.

PICKLING LIQUORS

Neutralization of sulfuric acid waste pickling liquors and subse-quent production of FeS04 leaves a residue containing CaS04 . A possible usefor this residue is as a binder. 39

PORTLAND CEMENT

A Russian patent 40 describes the use of portland cement or aluminacement, with or without the addition of sodium silicate, as a binder for abra-sive wheels of quartz, corundum, carborundum, and like materials.

POTASSIUM SILICATE PLUS Zn OR Ca COMPOUNDS

41A U. S. patent on the bonding of abrasives indicates that a stable,

heat-resistant binder that is self-setting at room temperature and resistantto discoloration in moist climates consists of a mixture of about 350 parts ofa high-ratio potassium silicate (Si0p>/K2 less than 2), about 100 parts of ZnO,ZnC03 , or CaC03 , and 1.5 to 2 parts of a wetting agent such as sulfonatedcastor oil.

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SALT HYDRATES

According to a German patent, 42 ores may be pelleted by mixing themwith a binder that consists of a supersaturated solution or melt of a hydratedsalt, of which the liquidus temperature is above room temperature.

SILICA

The preparation of colloidal silica sols in vhich the silica is ofvery small particle size has been described in a U. S. patent. 43 The use ofsuch sols, with gelation promoted by an acid or a "latent acid" (such as form-amide, which yields formic acid and ammonia on hydrolysis), has been recom-mended for the binding of ore pellets, 44 and may be of particular interest inpelletizing calcium fluoride for use in the steel industry.

SILICATES (See also Sodium Silicate.)

Granular lead oxides are prepared, according to a German patent, 45

by mixing FbO or FD3O4 with 5 to 15 percent of a wetting, binding, and harden-ing agent and heating the mixture to 300° C with a vibratory motion. Sodiumor potassium silicates are among the suitable agents listed.

SILICIDES

Carbon articles such as electrodes can be bonded together by appli-

cation of a collodion-acetone suspension of Si and/or one or more of such sui-cides as those of Mo, W, Ti, Zr, Ta, and Cr and heating to 1900° to 2100° C in

an argon atmosphere. 46

SILICON CARBIDE

Carbon articles were made by mixing amorphous carbon with SiC or an

inorganic carbide, molding, and heating to above the temperature of decomposi-

tion of the carbide. 47

SODIUM SILICATE (See also Silicates.)

A German patent 48 describes a process of preparing granular super-

phosphates from powder by adding 1 percent of water-free sodium silicate and

5 percent 7-hexachlorocvclohexane in the presence of 2 to 3 percent water end

mixing well in a granulating apparatus. The drying and setting process is

fairly rapid. The use of sodium metasilicate or other alkali silicates is also

described in a Spanish patent. 49

Sodium silicate has also been used with a variety of other materials

as additives. For example, a Japanese patent 50 calls for the use of a mixture

of 30 kg of commercial Na2Si03 , 1 kg of carnauba wax, 10 kg of water, 15 kg of

kieselguhr, 22 kg of CaCl2 , 17 kg of K2S04 , and 20 kg of talc powder. The mix-

ture is ground to -100 mesh. Use of 30 kg of this mixture with 200 kg of sand

and a suitable amount of water gives a molded product that does not freeze in

winter and is waterproof and fireproof.

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A U. S. patent 51 referring to the agglomeration of iron ores in theblast furnace describes the use of sodium silicate alone or mixed with molassesor glucose as a cementing agent to decrease the formation of flue dust in theblast furnace, and states that as little as 0.1 percent of 40° Be water glassmakes a measurable difference in flue dust formation.

For making fuel briquets, a German patent 52 describes the use ofsodium silicate containing citric acid.

A U. S. patent describes the binding of organic and inorganic mate-rials, including refractories. 53 This is done by dissolving tartaric, citric,or lactic acid in water to give a pH of about 2.5 and adding 1000 cc of thissolution to 20 to 30 cc of a solution of a polyhydric alcohol and 30 cc of aglucose sirup. This mixture is then added to 33*5° to 67.5° Be sodium sili-cate until a pH of 10 to 12 is obtained. Other binder compositions of asimilar nature also are described. The aggregate and binder are mixed, com-pressed, solidified at about 150° C, and fired at 1000° to I85O C. Thearticles possess good storage characteristics and are insensitive to frost.

W0LIAST0NITE

This native calcium metasilicate (CaSi03 ) was used in making abra-sive wheels. 54 The materials were heated to various temperatures, quenched,pulverized as needed, shaped under pressure, and sintered at 800° C. Decreas-ing the particle size and increasing the shaping pressure gave strongerarticles, but the compressive strength was decreased if the temperatures usedprior to quenching were increased from 1200° to l800° C.

ZINC SULFATE HYDRATE

Rapid setting and intense hardness were observed for binders con-sisting of anhydrous ZnS04 and water, but strength was lost completely underconditions that permitted the subsequent loss of water and reversion to theanhydrous salt. 55

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ORGANIC BINDERS

ALGINIC ACID

A German patent 56 on the manufacture of fuel briquets indicates thatthe molding properties of bituminous coals or petroleum or pitch semicoke canbe improved by the addition of alginic acid or its salts or gels. It can beapplied in the form of an emulsion with organic agglutinants such as tar, pitch,or anthracene oil, and the addition of milled soft pitch is recommended withlover volatile fuels.

ALKALI CELLULOSE

A German patent57 describes the preparation of weather-resistantbriquets by treating coal, coke, or wood charcoal with a 2 percent solution ofsulfided alkali cellulose, heating at 50° C, adding some water if necessary,and then pressing.

AMINES

According to a U. S. patent, 58 solid particles such as coal, fly ash,or ceramic materials that contain "digestible matter" may be bonded by mixingthem with amines such as RNH2, where R is aliphatic and contains not more than12 carbon atoms, or EsN(CE2)nWi2t where n is not more than 6.

ANTHRACENE-SULFUR

When anthracene oil was heated for 5 to 7 minutes at 280° to 290° Cwith 3 percent of sulfur, a binder suitable for use in making coal briquets wasobtained. 5 '-' When 0.1 to 3 percent of this binder was added to the coal charge,

briquets having improved strength and water resistance were obtained.

ARALDITE

The physical and chemical properties of Araldites (epoxy resins) as

binders have been discussed in two reports. 60 *61

ASPHALT

Because of a scarcity of tar in France, experiments on the use of

asphalt as a binder for briquetting fine coal dust have been carried out.62

A French patent63 describes in detail the preparation from a Kuwait

crude oil of an asphaltic bitumen that is suitable for use as a binder for coal

fines.

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The modification of petroleum asphalts by air oxidation at 2J5° to280° C to increase their viscosity and adhesiveness has been described in twoRussian articles; 64 * 65 such products are used in making coal briquets.

Asphalts with various additives have been used as binders. Forexample, a British patent66 calls for powdered casein and magnesium silicateto be stirred into melted asphalt ic material. Salt and sugar may also beadded. The resultant binder is suitable for use with rock aggregates forpavements.

A liquid binder, capable of coating damp or unheated aggregates,was made by blending 10 to 50 percent of a viscous, nonvolatile hydrocarbonoil with 20 to 60 percent of a volatile petroleum distillate and mixing theblend with 15 to kO percent of a powdered, hard asphalt; this is the subjectof U. S. patents.67

Another U. S. patent68 deals with the admixture of phenolic com-pounds and a metal oxide such as PbO with asphalt in the manufacture of bindersuseful in road construction.

Oleylamiee in amounts of approximately 2.5 percent added to asphaltimproves binding action, especially for acidic or moist aggregates. 69

The use of 0.1 to 5 percent of a substituted tetrahydropyrimidine(i.e., 2-heptadecyl-4,6,6-trimethyl-3,^,5>6-tetrahydropyrimidine) to improvethe binding characteristics of asphalt also has been patented in the UnitedStates, 70

Still another U. S. patent 71 involves the addition of a solvent toasphalt. The solvent is of the paraffinic hydrocarbon type, b.p. 50° to 200°

C, and the solvent action is increased by admixture of small amounts of oxy-genated solvents of the ether, ester, or ketone type.

BITUMENS

Numerous articles have been published on the use of various bitumi-nous materials as binders. Some of these deal with general features of bind-ing action, while others cite specific mixtures and applications. In one ofthe former type, 72 water resistance is discussed in terms of adhesion betweenthe mineral aggregate and the binder. Adhesion is defined as the resultantof the interfacial tensions of water and the binder relative to the aggregate.Negative values indicate that water tends to displace the binder, as it doeswhen the aggregate is hydrophilic. With positive values, the aggregate ishydrophobic and the binder is not displaced readily by water. Chemical inter-action between binder and aggregate is an important factor; the hydrophobiccharacter accompanying good adhesion is enhanced by reaction between basicoxides of the aggregate and acidic groups of the binder to give water- insolublecompounds.

In using bitumens instead of pitches as binders for fuel briquets,it is important to develop procedures that work best for the particular bitu-men used. 73 A Nagylenglyl crude oil bitumen, 74 although inferior to coal tarpitch for binding coal briquets, could be used satisfactorily, especially whenapplied in the molten state by spraying.

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According to a German patent, 75 ores, coal, lime, or mixtures thereofare briquetted with a distilled bitumen having a penetration (depth of penetra-tion of a needle of specified shape under controlled conditions of load, tem-perature, and time. See ASTM. Designation D5-52) of 20 to 30 at 25° C. Thepowdered material is wet, mixed with the hot liquid bitumen, and homogenizedbefore pressing.

Several shale bitumens were studied as possible binders for coalbriquets; those of lower density (about 1.1) and softening temperature (46°to $0 C) vere not satisfactory, but one with a density of 1.17 and softeningtemperature of 87 C produced briquets of high heat- and water-resistance thatwere superior in mechanical strength to those made with coal tar pitch. Anotherstudy of shale bitumens77 showed that those of high softening temperaturescould be used directly, while those of lower softening temperatures couldadvantageously be applied as pastes with lime.

Bitumen emulsions also have been much used as binders. Coal fines,for example, have been briquetted satisfactorily after being sprayed with anemulsion of petroleum bitumen, water, and an emulsifier; 78 pressing was at250 kg/sq cm while the material was hot, and the effects of varying the part-icle size, moisture content, amount of binder, and other factors were studied.

A U. S. patent 79 deals with the use of a quick-breaking oil-in-watertype of emulsion of bitumen for binding mineral aggregates. The bitumen isemulsified in combination with NaOH and an alkali metal phosphate. A similartype of emulsion used for bonding hydrophilic aggregates and incorporating 0.05to 0.5 percent of sodium dichromate is said to form a particularly strong bondwith the aggregate. 80

Another U. S. patent81 involves adding Na3P04 to a low-viscosity,quick-breaking, clay- free bituminous emulsion to slow down the breaking toallow sufficient time for mixing with the aggregate, fibrous filler, and othermaterials, while a French patent82 describes the use of such emulsions withthe addition of an emulsion-breaking agent to give controlled breaking at thedesired time, A general theoretical discussion of the adhesion of bitumens torock aggregates and the use of emulsifying agents has been published.83

Bitumens have been modified by the incorporation of various types ofadditives. A German patent84 claims improved adhesion of bituminous bindersto aggregates by the addition of small amounts (0.01 to 1.0 kg/1000 kg ofaggregate) of an aqueous dispersion containing, preferably, 10 to 15 percentof a water- insoluble amine or amide. For example, an especially useful dis-persion contained 75 percent water, 10 percent long-chain amine, and 15 percentof a 21 percent alkyl sulfate solution.

A French patent85 also calls for the admixture of amines to improvethe adherence of bitumen binders, citing RNH2 , RR'NH, and RR'R" N, where R, R 1

,

and R" are hydrocarbon radicals of at least 13 carbon atoms.

Two French patents86 ' 87 claim to improve the adhesiveness of bitumi-nous binders by the addition of 0.2 to 5 percent of salts of primary or sec-

ondary amines that do not decompose on heating, or 0.1 to 5 percent of reactionproducts of polyamines with mineral or organic acids. These salts may be addedas such or formed in situ by incorporating the acid and base separately into

the bitumen solution.

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A German patent88 specifies as a binder for making coal or cokebriquets a mixture of bituminous hydrocarbons, sulfidic benzene derivatives,sulfidic benzene homologs, and aliphatic halohydrocarbons. The componentswere mixed and heated in an autoclave while being stirred rapidly.

A blend of petroleum bitumen and a fraction from Ladkin asphaltitewas said to be thermally and chemically a more stable binding material thancoal tar pitch. 89

The addition of calcium phenolates to avoid the undesirable effectsof naphthenic acids in bitumens has been cited by a German patent. 90 Thus 51kg of CaO was dissolved in 8.5 metric tons of boiling commercial creosote oilwith simultaneous removal of 25 kg of water (and a small amount of oil) bydistillation. After cooling, the oil was added to 4l.5 tons of bitumen "B-80"and stirred at 150° C. Adhesives of the amine type were then added.

A French patent91 describes the preparation of bituminous bindershaving good adhesion toward mineral aggregates and metals. In the process,0.5 to 2.0 percent of heavy metal soaps of high molecular weight organic acids,such as Fe or Fb oleates or naphthenates, was added to the bitumen. Thisbinder was used as a preliminary coating; a further quantity of binder notcontaining such soap was then added.

The addition of unslaked lime to bitumen to produce a slow- settingbinder is described in a U. S. patent. 92 Another U. S. patent93 covers theuse of a heavy bitumen to which an organic nitro compound has been added formaking carbon electrodes.

The improvement of adhesiveness of bituminous binding agents by theaddition of organic silicon compounds, such as (CH3)x (CH30)ySi, where x + y = k,

is claimed in a German patent. 94 The silane may be applied to the rock aggre-gate prior to addition of the binder, or it may be mixed with the bitumen.

BUTADIENE- CHL0R0PRENE

The bonding of abrasive articles by the use of polymerized chloro-prene mixed with a butadiene monomer and an unsaturated ketone has been claimedin a U. Sr patent. 95

CARBOHYDRATES (See also Cellulose Derivatives and Starch.)

The preparation of carbohydrate ethers or esters for use as bindershas been described in a U. S. patent, 96 and carubin (locust bean gum), whichis about two-thirds mannose and one-third galactose and almost completelywater-soluble, has found application as a binder in the ceramic and miningindustries. 97

CASEIN

A mixture of casein with 30 percent by weight of portland cement hasbeen patented in Russia as a binder for making abrasive wheels. 98

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CASSAVA FLOUR (See Manioc Flour; Sulfite Liquor, and reference 177.)

CELLULOSE DERIVATIVES

A German patent" describes the preparation of a polysaccharide bind-ing agent, suitable for use in textiles, papers, and paints, from inorganicreactants and cellulose derivatives. For example, 25 parts of sodium carboxy-methylcellulose, 10 parts of A12 (S04 )3 , and 5 parts of Ca(0H)2 or 3 parts ofMgO form a useful dispersion when added to water and stirred.

COAL PLUS AMINES (See also Amines; reference 58.)

A mixture of coal and amines has been patented in the U. S. 100 as abinder for ceramic materials. It i6 hardened by heating it to a temperaturebelow the decomposition temperature of the coal used.

COAL HYDROGENATION PRODUCTS

According to a Russian patent* * the product obtained by hydrogenatinga humus coal at 350° to 380 C and 50 to 100 kg/sq cm may be used as a binderfor briquetting coal.

DRYING OILS PLUS ADDITIVES

A British patent102mentions a number of drying oils (for example,linseed, soybean) which may be mixed with about 15 percent Isano or Boleko oil,heated to the desired viscosity (5000 cp at 20° C, for example), treated with0.1 percent Co and 0.3 percent Fb driers, and used in about 2 percent amountswith quartz sand to make foundry cores.

EPOXY RESINS (See also Araldite.)

A German patent103 claims that resins made by curing epoxy alkylesters of polybasic aromatic acids with polycyclic aromatic amines can be usedas bonding agents for metals and other materials. For example, 100 g of di-glycidyl terephthalate melted with 25 g of benzidine was heated at 90° to 100°

C and degassed for 5 minutes at 5 to 20 mm, poured into molds, and cured at 1^0°

C for 60 minutes.

Another patent104 describes a cement for abrasives that is made bythe condensation of vinylcyclohexene dioxide wdtto pyrome11itic anhydride.

A U. S. patent105 describes a binding mixture of 5 parts by weight ofan epoxy resin prepared by the reaction of 2,2-bis(4-hydroxy-3-allylphenyl)pro-pane and epichlorohydrin, 3 parts of a high molecular weight (3,000 to 10,000)polyamide prepared by the reaction of dilinoleic acid and ethylenediamine, and

1 part of a liquid polysulfide prepared by the reaction of bis(2-chloroethyl)~formal and Na2Sx cured for 10 to 12 seconds at l80° C. This had excellent

strength and good resistance to water and ethylene glycol.

- 16 -

FURAN DERIVATIVES

A U. S. patent106 claims that molding sands or abrasive granules may-

be bonded with k percent of a mixture such as 75 parts of furfuryl alcohol,

25 parts of maleic anhydride, 5 parts of urea, and 0.5 part of NH4CI. Theresulting mix was cured in an oven at 300° F.

GLYCEROL

A German patent already cited45 describes the preparation of granularlead oxides by mixing the oxide (FbO or Fb3 4 or both) with 5 to 15 percent ofa wetting, binding, and hardening agent and heating them to 300° C with a vi-bratory motion. Glycerol, as well as dispersions of high polymers (e.g., pol-yvinyl chloride in acrylic acid or polystyrene, sulfite liquor or molasseswastes), is listed as a suitable additive, Glycerol also may be used as abinder in refractories and ceramic-bonded abrasive compositions. 107

GLYCOL ESTER DERIVATIVES

A binder for uniform, very hard, dense, abrasive forms is made froman unsaturated polymer of a glycol and an unsaturated polybasic acid, copolym-erized with a vinyl monomer and styrene in the presence of benzoyl peroxide(U. S. patent). 108

GUMS, NATURAL (See Shellac.)

HUMIC ACID AND HUMATES

A Russian patent109 describes a binder for coal briquets that is

obtained by treating brown coal ground to 0.5 mm particle size with a 0.1percent solution of NaOH or NH40H. This is similar to the preparation des-cribed 15 years later as "new'

;— a sodium humate made by fine grinding of coalin an alkali; 77 the amount of this used in briquetting xras kept below 1.5 per-cent to avoid tackiness on the press.

Other experiments on the use of humate s as fuel briquet binders110

indicate that the crushing strength of the pro:.:ct depends upon the cationaccompanying the humate ion; with Na a mar-rimum of i+0 kg/sq cm is attained,but with Al, NH4 , Fe, and Ca it is 20 kg/cq cm or less. Optimum amounts ofthe binder are 3 to 6 percent.

EYDR0XYAMINE DERIVATIVES

A British patent111 describes binding agents for tar and bitumenthat are made by treating (H0C2H4NHC2H4)2NC2H40H with stearic or oleic acidat 140° to 160° C.

- 17 -

LIGNOSULFONATES

A study of the variation of properties of lignosulfonates with vary-ing molecular weights showed that with increasing molecular weight their bind-ing strength in iron ore pellets increased. 112

LUPINES

A Hungarian patent113 specifies that if seeds of lupines or soybeansare steeped in an acid solution for 8 to 12 hours, separated from the liquid,disintegrated, partly freed (if desired) of their oil content, and added to pow-dered coal in amounts of 1.5 to k percent, suitable binding action is achieved.

MANIOC FLOUR PLUS MOLASSES

A French patent114 describes the binding of charcoal briquets with amixture of 560 g of manioc flour, I+33 g of molasses, k g of 30 percent NaOHsolution, and 3 g of 30 percent formaldehyde solution.

MOLASSES

A French patent115 dealing with coal briquets describes as the binderused a hardened product obtained by dehydration of molasses or other sugar res-idues followed by polymerization at an elevated temperature in the presence ofa catalyst. The brittle product is then ground to a powder, which may be usedalone or mixed with tars, bitumens, resins, or with a fermentation inhibitor.

NITROPHENOLS

Although the nitrophenols are apparently not used alone as binders, aJapanese patent116 claims that the addition of a "phenylnitrophenol compound"to a binder for the manufacture of molded products of carbon and graphite im-

proves their hardness and bending strength.

ORGANOSILICONS

A U» S. patent117 claims polymers of siliconols, alkoxysilicons, sil-

iconacylates and other organosilicons as binders for abrasives. They may be

used with or without nonsilicon resins.

PETROLEUM OXIDATION PRODUCTS

Binders that have kerosene or white spirit oxidation products as their

base are prepared by the oxidation of hydroxy acids with xylitol or its anhy-

dride in the presence of H2S04 , NaHS04 , or a sulfonic acid to thicken the pro-

duct. Drying of the esterification product is hastened by dissolving it in

solvent naphtha containing 1 to 2 percent litharge (Russian patent). 118

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PETROLEUM PITCH

A binder described in a French patent119 is composed of a mixture ofpetroleum pitch and coal tar stabilized with bituminous shale pitch.

A British patent120 describes a petroleum pitch suitable for makingcoal briquets. The pitch is made by air oxidation of a residue from the vacuumdistillation of petroleum (or a bitumen obtained by deasphalting such a residue)at 3^0° to 400° C and atmospheric pressure. Steam injection is used to controlthe temperature, sweep out volatile substances, and prevent the deposition ofcoke. .

-.;.

A U. S. patent121 deals with binders for carbon electrodes; thesebinders (softening point 70° to 120° C, specific gravity 1.2 to 1.3, and H/cratio less than l) are prepared by mixing a cracked petroleum fraction, con-taining at least 50 percent by weight aromatic compounds and having a min-imum boiling point of 650° F, with a partially hydrogenated cracked fractionalso containing at least 50 percent aromatic compounds and having a minimumboiling point of 700° F. The mixture is then thermally and noncatalyticallycracked at 100 to 2500 lb/sq in. gage and 800

ato 1000° F, and the product

stripped at less than 525° F and 20 mm pressure to produce the binder.

Binders useful as substitutes for tar in the manufacture of solidfuels are described in a French patent; 122 they are made by mixing coal dustof 0.5 to 1 mm particle size with petroleum pitch and, optionally, oil tar,

Al2(S04 ) 3 , and an oxidic mineral containing 8 percent carbon, 6 percent Fe203 ,

31 percent A12 3 , 48 percent Si02, and 7 percent IfeO.

PHENOL-ALDEHYDE RESINS

In the preparation of phenol-aldehyde resin binders, various phenoliccompounds or crude phenol-containing mixtures and various aldehydes have beenused. • An example of the application of a crude mixture is seen in a Frenchpatent.

1' To 1000 kg of a crude wood tar containing 3*5 percent acetic acid,

ammonia was added in sufficient amount that 10 to 15 kg of acetic acid remainedunneutralized. This provided a mixture of acetic acid and its ammonium salt

to serve as a catalyst for the condensation reaction. Then 70 kg of acetal-dehyde was added slowly, with stirring, under an atmosphere of nitrogen, the

temperature was raised slowly to 70° C and maintained at that point, withstirring, for 5 hours. A slow stream of air was then passed through the massand the temperatuz-e raised to about 110° C. After 14 to 16 hours, a productwas obtained that softened at about 60° C, melted at 71° C, and was useful as

a binder for coal dust.

A binder for charcoal briquets described in a Japanese patent124 wasmade by heating a mixture of 100 parts crude phenol, 100 parts formalin, and2 parts H2SO4 for 1 hour at 60° C, washing with an equal amount of water,allowing the residue to stand 2 hours with 100 parts of methanol and 5 partsof 38 percent NH40H and then overnight with 10 percent NaOH in methanol.

A British patent125 involves the use of formaldehyde with a coal taracid fraction containing phenol (phenol: formaldehyde ratio of 1:1.5 to 1:2.2)and condensation in aqueous NaOH. Lignin, starch, cellulosic material or othercarbohydrates may be used as extenders, and the coal briquets are cured byheating to 1^0° to 160° C. The briquets are weather- resistant.

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A modified phenol- formaldehyde resin, containing about 10 percent ofo-chlorophenol, is claimed as a binder for abrasives in a U. S. patent. 126

A British patent127 claims that the bonding of such materials as glassfibers by means of a phenol-aldehyde resin can be greatly strengthened by in-corporating 0.1 to 0.5 percent of an organosilicon compound of the formula%SiX4.n , where R is an alkyl, aryl, or alkylaryl radical containing one ormore OH or Wis groups reactive with the resin, X is alkoxy, aryloxy, OH, or ahalogen, and n is 1, 2, or 3.

A Russian patent128 relates to the use of a mixture of powdered phenol-formaldehyde resin and rubber for bonding grains in making abrasive articles,and a U. S. patent 1 9 describes the bonding of metal oxides or magnetic com-positions by the use of a 2:1 mixture of phenol- formaldehyde and urea-formal-dehyde resins along with Ca, Zn, or Bu stearate, carbowax plasticizer, and alittle water.

PHENOL BORATES AND PHOSPHATES

The bonding of abrasive grains in making grinding wheels may be accom-plished, according to a U. S. patent, 130 by means of boric and phosphoric acidesters of various phenols. In one example a resin was made from 12.1 parts ofmonophenyl phosphate, 11 parts each of resorcinol and hydroquinone, and li.3parts of boric acid. The mixture was refluxed to drive off water, and the tem-perature was gradually increased to 200° C within an hour to yield a brown,somewhat pliable, sticky resin. The resin was mixed with 2 percent hexa-methylenetetramine, and carborundum grains added until the resin was 10 percentof the mixture. This was formed into a wheel, cured 1 hour at 175° C and thenat 200° C.

PITCH (See also Petroleum Pitch.)

Various pitches and pitch combinations have found extensive use asbinders, probably because of the ready availability and low cost of the pitchas well as its desirable physical and chemical properties. Although a majorityof these applications seems to be in the realm of making fuel briquets, the useof pitch as a binder is by no means restricted to these materials.

According to a British patent, 131 a binder is produced by oiling backa pitch, removing water and part of the oils by distillation, extracting with a

solvent to remove certain undesirable constituents, and distilling off the sol-

vent .

High-boiling fractions from pitches and tars, together with the sec-

ond anthracene fraction obtained in pitch rectification (softening temperatures69° to 83 C, 19 to 33 percent insoluble in toluene, and 71 to 77 percent vol-

atile) show promise as bonding agents for coal briquets. 132 Average softeningtemperatures of such pitches rose from 79° +-0 101° C during 12 months, whilethe volatile contents dropped slightly, frcn 73.3 to 71.4 percent. Briquets

bonded with 12 percent of pitch at 150° C and pressed at 95° C and ^00 kg/sq cmpossessed high mechanical and water resistance and were not tacky.

- 20 -

A German patent133 specifies a mixture of hot pitch, dispersibleclay, water separated during the purification of gas, and 0.5 to k- percentnaphthalene, anthracene, or phenanthrene , as a suitable binder to be trituratedwith coal in making briquets.

Another patent134 describes the briquetting of wet coal sludge by-

mixing it with 5 percent of a liquid pitch-coal product obtained by heatingfluxed hard pitch and powdered coal up to 300° C,

The use of wash oil or lignite tar oil and pitch in briquetting solidfuels is claimed in another German patent. 135 Still another136 applies to theuse of tar-pitch melts as binders for fuels that are not easily coked, and aremoist and fine grained.

Lignite pitch as a binder for the briquetting of crushed solid fuelsis specified in another German patent. 137

A discussion of the optimum properties of pitches, the addition of20 to 30 percent pitch distillate to promote better covering of the coal par-ticles, the use of pitch emulsions and of air-blown pitch distillate has beenpublished. 138 Laboratory experiments have shown it possible to prepare sat-

isfactory briquets by adding 8 percent or more of coal tar residue with amelting point of 95° C to coal fines. 139

A German patent140 describes the use of tars and pitches from thelow-temperature carbonization of brown coal as binders for briquetting coaland other solid carbonaceous fuels.

The influence of the chemical and physical properties of pitch onits binding characteristics has been studied, 141 with special attention tothe role of the gj, P, and 7 constituents, (Note: the a fraction is thatportion insoluble in pyridine; the P fraction is soluble in pyridine but in-

soluble in chloroform; and the 7 fraction is soluble in both pyridine andchloroform-G*R»Y.) The content of the £ and 7 components should be about 80percent and their ratio 1:1. Low-quality pitch contains high amounts of a and7 components. In this study, the ductility of the pitch was stressed.

A technique has been developed whereby the pitch binder in a coalbriquet can be made visible and the amount used can be estimated by micro-scopic examination. 142

A study of medium- soft pitches from coke oven, horizontal retort,vertical retort, and low-temperature tars has been made, using infrared anal-yses, solvent extraction, and chemical analyses. Physical properties wererelated to viscosity, and specifications for pitch as a binder for briquetsand carbon electrodes were reviewed. 143

A further study of binders by a viscosity measurement (the torquerequired to rotate a platinum disc dipped into the molten sample) at temper-atures between 40* and 1^0° C has included hard pitches.

144Agglomerating

properties were evaluated by determining the compression strengths of pitch -

coke briquets made with the binders. Values obtained with the pitches wereabout as might be expected on the basis of industrial experience.

- 21 -

Various additives have been used with pitches in the preparation ofbinders. A U. S. patent145 relating to the making of carbon or graphite elec-trodes specifies the use of less than 5 percent of an additive with pitch, orwith a tar which is subsequently distilled until an 80° C softening pointis attained. Suitable additives listed are MnCl3 , CrCl3 , FeCl3 , nitrobenzenesulfonyl chloride, p-toluene sulfonyl chloride, or nitronaphthalene sulfonylchloride.

A Japanese patent 146 mentions the use of coal-tar pitch and resin infish oil or mineral oil, dispersed by means of an alkaline solution of cellulose,as a briquet binder.

Making refractories of calcined dolomite and a binder of 65 to 70percent coal-tar pitch and 30 to 35 percent anthracene oil and pressing at morethan 500 kg/sq cm has been described. 147

A German patent 148 describes bonding carbon articles together or tometals with a mixture made up of one-third pitch, one-third electrode graphite,and one-third graphitic acid.

A German patent 149 involves mixing tar oils and wood or lignin withpitch to obtain binders with a wide plasticity range. For example, 1000 kg oftar pitch was heated until the softening point rose to above 100° C, and then85O kg of anthracene oil and 300 kg of lignin were added. Heating was continued

3 to h hours to decrease the point of fracture.

Hard spherical coal pellets for subsequent activation with steam at1750° F were described in a U. S. patent; 150 they were made by mixing the pul-verized coal with 20 to 30 parts of core pitch and tumbling the pellets withk-0 cc per 100 g of powder of a molasses solution of specific gravity 1.10 to

1.15.

A German patent151 describes the use of an emulsion or suspension ofpitch, prepared with the aid of such an emulsifying agent as concentrated sul-

fite liquor, as a binder for briquetting carbonaceous fuels; a Japanese patent152

claims what appears to be a similar mixture made up of 25.5 parts of coal tar,

U8.3 parts of coal tar pitch, 25.4 parts of water, 5 parts of 30° Be waste pulp

liquor, and 0.1 part of NaOH mixed together at 95° C.

POLYACKYLAMIDE

Polyacrylamide is a water-soluble, nonionic powder made by the polym-

erization of acrylamide. In aqueous solutions it is compatible with most natu-

ral and synthetic water-soluble gums, latex systems, and many salts; it is a

good thickening agent, protective colloid, and binder. 153

POLYALKYLENE GLYCOL-POLYETHYLENE OXIDE

The binding of precious- stone abrasives with a polyalkylene glycol-

ethylene oxide polymer is described in a U. S. patent. 154 For example, 20 g of

diamond or sapphire powder was dispersed with $k g of polyalkylene glycol and

agitated while 26 g of ethylene oxide was added; heating and stirring were con-

tinued until a uniform consistency was obtained. The polymer had a molecular

weight of 4000 and melted at 50° C.

- 22 -

POLYAMIDES

Magnetic cores, described in a French patent, 155 were made by emul-sifying a superpolyamide with 80 percent ethanol in an autoclave at 1 kg/sq cmpressure and 120° C, mixing with a magnetic powder such as iron, homogenizingin a heated mixer, coagulating with cold water, and homogenizing again.

POLYESTER RESINS

A U. S. patent156 describes a binder that may be used for abrasivesand other materials. A mixture of k.k parts of ethylene glycol, Ml. 7 partsof commercial pentaerythritol, 21.5 parts of a diallyl ether mixture ofpentaerythritol, 22.3^ parts of maleic anhydride, 2.3 parts of boric acid,and 18.6 parts of water was heated under COs and stirred at 170° to 190° C

for 3 hours. The product had an acid number of 17 .^; it was diluted withwater to 75 percent solids prior to use.

POLYMERS OF HYDROCARBONS

A Dutch patent157 describes the use of various polymers and/orcopolymers of olefinic hydrocarbons, their mixtures, and their mixtures withpitch. Monomers listed as suitable starting materials are ethene, propene,butene, butadiene, and styrene. The binders were used in making fuel briquets.

POLYURETHANES

A U. S. patent 158 gives the details of preparing elastic grindingarticles. In an example, 600 g of AI2O3 was moistened with a solution of10 percent of hfk 1

, V-tri-isocyanatotriphenylmethane in CH2CI2, the solventevaporated and the A12 3 added to a molten, castable polyurethane polymer,stirred vigorously for 30 seconds, and the mixture placed in molds for 2khours. The polyurethane was prepared by adding 70 g of 1,4-butanediol to thereaction product of 1000 g of linear polyesters containing aliphatic OH groupsand 300 g of 1,5-naphthalene diisocyanate and stirring for 30 seconds.

POLYVINYL ACETAL

A bonding composition for magnetic metal described in a U. S. pat-ent159 consists of ^2.5 percent of polyvinyl acetal (obtained by the reactionof 70 percent hydrolyzed polyvinyl acetate with acetaldehyde), ^2.5 percentof polyvinyl acetate, and 15 percent of a B-stage condensate of cresylic acidand formaldehyde.

PRICKLY PEAR LATEX

A latex can be obtained by pressing prickly pears; when mixed withsulfur and heated under pressure this forms a binder. It is not water-resistant. 160

- 23 -

RESINS

«v ;, SiUS

?of

„8ynthetlc re?ins as binders for magnetic granules has been

described, 161 and a German patent"* deals with the use of such resins in bind-ing fuel briquets.

Another German patent163 describes water-resistant binders, useful forabrasives, which were made from novolak-hexamethylenamine and coal tar pitchthat had been modified by blowing.

SAWDUST

An Austrian patent164 claims that briquets can be made from coal whichalone is not amenable to briquetting (e.g., brown coals) by mixing it with 20 to50 percent of sawdust or similar wood waste and pressing at 1200 to 3000 atmos-pheres.

SHALE BITUMEN

Heating Baltic shales up to about 380° C converts much of their or-ganic matter to an extractable form, called pyrobitumens . These pyrobitumensshowed good binding properties when used for the briquetting of fine coal. 165

SHELLAC

The use of shellac for binding abrasive articles has been patented inthe United States. 166

SOYBEANS (See Lupines and reference 113.)

STARCH

Various starch preparations, derivatives, and mixtures have foundnumerous applications as binding agents. As a binder for fuel briquets, a U. S.

patent167 claims a solution of 100 grams of potato starch dextrin in 1 liter ofwater which was heated while 100 ml of glacial acetic acid was added. Otherorganic acids may also be used. A rather similar procedure is given in a Dutchpatent, 168 which claims that this binder permits the use of much lower pressuresfor briquetting than those permitted by pitch binders.

Another U. S. patent 169 gives a process that calls for further addi-tives. Twenty kg of potato starch was mixed gradually with 2.7 kg of 80 percentacetic acid and the mixture heated to 175° C. A mixture of 2 kg of polyvinylacetate and 2.5 kg of 80 percent acetic acid heated to about 60° C was added tothe first mixture, and 0.6 kg of paraffin also was added. This mixture wascarefully and thoroughly mixed with 1000 kg of coal dust containing 11 percentH2O, the temperature raised to 90° C by steam injection, and the briquets pressedand air dried. They were resistant to outdoor storage and did not disintegrateduring burning.

- 2k -

The use of starch in the presence of alkalis also has been appliedto making fuel briquets. A British patent 170 dealing with the making ofbriquets from peat that had been treated with alkali does not, however, claimthe starch as a binder, but says that a small quantity of starch is incor-porated before, during, or after the alkali treatment in amount insufficientto act as a binder but sufficient to replace the lost colloidal substancesof the peat.

Another British patent 171 says that a binder for fuel briquets wasprepared by mixing starch, water, and an alkali such as Na2C03 or WaOH andheating the mixture to 220° to 350° F to produce a heavy, viscous, stickyfluid. A U. S. patent172 claims the production of a material suitable foruse as an adhesive or a binding agent from potato starch, sodium chloroacetate,and barium hydroxide.

A Belgian patent173 specifies as a binder a product obtained byesterifying starch at 60° to 300° C with 1 to 20 percent of an inorganic acidin the presence of 5 to 50 percent of urea and treating it with 5 to 50 percentof an aldehyde at a pH of 6 to 9« Curing may be done at 20° to 200° C.

A U. S. patent174 describes the preparation of a binder for variousmaterials. Five hundred parts by volume of a 40 percent solution of formal-dehyde was diluted with an equal volume of water containing 20 parts by volumeof 80 percent acetic acid; 500 parts by weight of potato starch was suspendedtherein and the mixture maintained at room temperature several hours prior touse.

STYRENE POLYMERS

A German patent already cited45 (see Glycerol) mentions the use ofpolystyrene.

A copolymer of styrene and linseed oil is described in anotherGerman patent175 as a suitable binder for coating formulations. A mixture of

900 g of styrene, l8 g of di-tertiary butyl peroxide, and 1.8 g of sulfurizeddipentene was added over a period of 2 hours to 1100 g of stirred linseed oilat l80° to 200° C. The sulfurized dipentene was obtained by heating 100 g ofdipentene and 5 g of sulfur at 150° to 250° C.

SULFITE LIQUOR

The reclamation of dust from the abrasion of lignite briquets is

the subject of an East German patent. 176 The dust was mixed with 2 to 5 per-cent sulfite waste liquor (31° Be) at 50° C and processed on a conventionalextruder. The resulting briquets had strengths up to 80 kg/sq cm.

Low-temperature carbonization of coal briquets for which h to 6

percent of beech wood sulfite liquor or 1.9 to 3 percent cassava flour wasused as the binder has been described. 177

A Russian patent178 on the briquetting of coal describes a binderconsisting of sulfite liquor and 3 to 5 percent of oxidized petrolatum, anda German patent179 claims the use of sulfite liquors added to the fuel before

- 25 -

or simultaneously with a tar-pitch melt to give briquets that may be renderedweather- re sist ant by heating at 150° to 200° C.

TAR

Tars of various kinds, like bitumens and pitches, find many applica-tions as binders. Often there is no clear-cut distinction between these mate-rials.

In one study, a horizontal retort tar was brushed on various testpieces of rock. After an hour these were immersed in Na2C03 solutions of knownconcentrations. The concentration of Na2C03 required to strip the tar from thetest piece in 24 hours at room temperature was a measure of the adhesion. Thefollowing qualitative estimates of adhesion to each rock type are given: ortho-clase - bad; hornblende - bad; biotite - poor; quartz - poor; labradorite -poor; augite - good; Olivine - excellent.

Low-temperature tars from peat and brown coal generators, low in aro-matic s content, were blown with oxygen at 200° C for 2 to 7 hours to raise thesoftening points; when used in amounts up to 7 percent of the dry fuel theywere satisfactory binders for briquetting bituminous and anthracitic coalfines. 181

A wide variety of tars and tar mixtures was studied in a search forbinders for anthracite fines. 182 These included petroleum residues, hydrogen-ation residues, coal tar, generator tar, wood tar, and others; over 100 exper-iments were carried out.

A German patent183 describes the modification of tar by heating it to150° to 350° C with oxygen-producing substances that leave no undesirable impu-rities, e.g., (M4 )2S208 (ammonium peroxydi sulfate) or activated carbon, priorto use as a binder for coal. This treatment is claimed to increase the contentof pyridine- and benzene-soluble components and thus increase the adhesive powerof the tar.

A review of the physical and chemical properties of tars and pitchesand their effects on binder performance has been published. 184

A study of the effects of water in tar binders has shown that binderconsumption may be reduced by determining the optimum water content, by loweringthe surface tension of the water by adding such agents as benzyl alcohol orsoap, and by using water-tar emulsions. 185

A Japanese patent186 claims good binding properties (for fuel briquets)

for a binder consisting of an emulsion of 50 percent of a mixture of 1 partminus 60 mesh coal and h parts coal tar heated 2 hours at 300° C, 15 percentcoal tar, 8 percent 30° Be' waste pulp liquor, and 27 percent water, mixed and

applied at 90° C.

Tar mixtures, useful in binding rock aggregate such as that used in

road building, are specified in a French patent187 as 40 to U5 parts of tar and

60 to 45 parts of a 300° to 36O C anthracene oil fraction.

- 26 -

Lime-treated tars are used in making binders for road surfacing

materials and for briquetting some coals, and a study of the physical changes

that accompany the addition of the lime has been published. 188 Making calciumcarbide briquets with 20 to 23 percent of a binder containing U5 percent coal

tar and 55 percent coal tar pitch is more satisfactory than using pitch alone.189

The use of wood tar from wood chemical plants as a binder for makingcharcoal briquets has been described. 130 The charcoal and wood tar were groundtogether, heated to 110° to 120° C, pressed at 65 to 300 kg/sq cm, and baked at^20° to 450° C for 35 to h0 minutes.

TARTRATES

In using chromium compounds in the binding of dead-burned magnesite,a strong, dense, crack-free mass is obtained by adding 0.25 to 2.5 percent ofan alkali metal tartrate and firing the mixture at 2800° to 2910° F. (See

also Chromium Compounds under Inorganic Binders, and reference 16.)

UREA-FORMALDEHYDE RESINS

Modified urea- formaldehyde or phenol- formaldehyde resins with im-proved bonding strength characteristics are produced by making a precondensatewith a predetermined methylol content and treating it with a mixture of fur-fural and furfuryl alcohol in the monomeric or semipolymerized state. 191 Theviscous resin so obtained is useful in making abrasive articles.

VINYL POLYMERS (See also Glycerol, reference ^5; Glycol Ester Derivatives,reference 108.)

A U. S. patent192 deals with the use of latex materials for bindingabrasives. These latexes were made by the emulsion polymerization of a vinylchloride-vinylidene chloride mixture, or a styrene-butadiene mixture. Onelatex, for example, contained 75 percent vinyl chloride and 25 percent vinyl-idene chloride. The latex was added to the grit, such as SiC, mixed, and thewater evaporated to leave free-flowing granules that were then placed in molds,pressed, and heated at 600° C for J>6 hours to form the abrasive articles.

A French patent193 specifies the bonding of abrasives with one ormore polymerized vinyl compounds that contain sufficient OH groups to besoluble or dispersible in water. This may be a polyvinyl alcohol, a partlyhydrolyzed polyvinyl compound, or a polymerized vinyl ester of a hydroxy acid.

ZAHLIT

Zahlit-D is an unsaturated hydrocarbon fraction with a specificgravity about 1 and Engler viscosity of 1300° at 50° C and 12.5° at 125° C.It is used, according to a Belgian patent, 194 as a binder for mineral fibers,for mica and asbestos to form insulators, or for lead salts to form bricksfor radiation protection.

27

REFERENCES(Abbreviations of publications in these references are those

used in Chemical Abstracts .)

1. Bugosh, John. Articles coated with fibrous boehmite. U. S. patent3,013,901, Dec. 19, 1961; C. A. 56, 10419h.

2. Anon. Theory of binder action and film formation. Baymal colloidalalumina. E. I. du Pont d.e Nemours and Co., Industrial and BiochemicalDept., Wilmington, Del. [Not dated but presumably issued about 1961.—G. R. Y.]

3. Levai, Marcel. A crystal- like binding material of relatively greathardness. Hungarian patent 135,524, Apr. 25, 1949; C. A. 45, 4854h.

4. Pechiney-Compagnie de produits chimiques et electrometallurgiques.Binder for aluminum nitride. French patent 1,223,202, June 15, 1960;C. A. 55, 19180c.

5. Sheets, H. D., Bulloff, J. J., and Duckworth, W. H. Phosphate bonding of

refractory compositions. Brick and Clay Record, v. 133, no. 1, p. 55-57

(1958); Refractories J., v. 34, p. 402-406 (1958); C. A. 52, 15865f.

6. Mitchell, W. J., and Moore, W. F. Zeolitic molecular sieves. Germanpatent 1,055,515, Apr. 23, 1959 (to Union Carbide Corp.); C. A. 55, 10749f.

7. Lyubomudrov, V. N. Use of borate glass as bonding material for abrasivedisks. Abrazivy, 1953, no. 6, p. 3-9; C. A. 49, 6561i.

8. Lyubomudrov, V. N. Boron aluminate as a bond in abrasives. Dokl. Akad.

Nauk S.S.S.R., v. 66, p. 89-90 (1949); C. A. 43, 6801i.

9. Compagnie des meules Norton (Soc. Anon.). Agglomerated granular material.

French patent 817,978, Sept. 15, 1937; C. A. 32, 23084

.

10. Vasenin, F. I. Chromium-calcium compounds and their binding properties.

Tsement, v. 5, no. 10, p. 36-33 (193^; C. A. 33, 19063 .

11. Zhuravlev, V. F. Calcium orthogermar ate and its binding properties.

Dokl. Akad. Nauk S.S.S.R., v. 59, p. _i45-1148 (1948); C. A. 42, 7186f.

12. Abramovici, R., Kohn, D., and Iakabfi, A. Abrasives with calcium oxide

as the binding agent. Rev. chim. (Bucharest), v. 9, p. 250-253 (1958)

(English summary); C. A. 54, 6073d.

13. Emhiser, D. E. Refractory compositions and binding agents therefor.

U. S. patent 2,793,128, May 21, 1957 (to Pittsburgh Plate Glass Co.);

C. A. 51, 12461c.

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14. Ottemann, Joachim, Solution and hydration of anhydrite. Anhydrite as a

binding medium. Abhandl. Geol. Landesanstalt (Berlin), no. 219, p. 1-16

(1950); C. A. 45, 2171a.

15. Socie'te de sondages, injection, forages (Ancienne entreprise P. Bachy).Silico-aluminous binders. French patent 817,397, Sept. 1, 1937; C. A. 32,23 16-*.

16. Chantler, L. W. , and Hund, W. 0. Organic binders for dead-burned magnesite.U. S. patent 3,030,216, Apr. 17, 1962 (to Martin-Marietta Corp.); C. A. 58,331e.

17. Suzuki. Hiroshige. Effect of clay binders on the oxidation of sinteredsilicon carbide bodies. Yogyo Kyokai Shi, v. 67, p. 221-226 (1959);C. A, 54, 14615d.

18. Mirskii, Ya. V., and Mitrofanov, M. Manufacturing molecular sieve syntheticzeolites in the form of microspherical powders. Dolcl. Akad, Nauk S.S.S.R.,v. 141, p. 1155-1157 (1961); C. A. 56, 13794g.

19. Dohmen, Heinrich. Pelletization of fine ores. German patent 1,124,705,Mar. 1, 1962; C. A. 57, 479g.

20. Capell, R. G., Amero, R. C, and Wood, W. H. Fuller's earth as a binderfor catalysts and absorbents * Petroleum Refiner, v. 25, no. 2, p. 69-71

(1946); C. A. 40, 25955 .

21. Kuzmick, P. L. Binder for diamond abrasives. U. S. patent 2,866,698,Dec. 30, 1958; C. A. 53, 6570c.

22. Anada, Naoaki. Liquid briquet binder. Japanese patent 1140(1950),March 31; C. A. 46, 7744d.

23. Kainarskii, I. S., and Dudavskii, I. E. Dinas with ferruginous binder.Ogneupory, v. 10, no. 6, p. 3-10 (1945); C. A. 42, 5637i.

24. Willmann, Karl. Fine-grained binders from coarse-grained limestone orother carbonates. German patent 1,092,367, Nov. 3, 1960 (to RhelnischeKalksteinwerke G. m. b. H.); C. A. 55, 26386b.

25. Volzhenskii, A. V. Semi-plant investigations on the production of a

binding material from burnt lime and gyps'-im. Prom. Stroitel. Material.,v. 2, no. 8, p. 37-40 (1940); C. A. 35, 3410e .

26. Tagaya, Masao, Nakamura, Nobuo, and Nobutr.ka, Shingo. Dolomite hearthlining. Tetsu-to-Hagane, v. 36, p. 2-4 (1950); C. A. 45, 69781.

27. Drozdov, K. S. Magnesium bonding material. U.S.S.R. patent 107,129,Aug. 25, 1957; C. A. 52, 3297a.

28. Kuznetsov, A. M., and Mikhailov, N. N. Comparative evaluation of thebinding properties of caustic magnesite and caustic dolomite. ZhurnalPriklad. Khim. (J. Applied Chem. U.S.S.R.), v. 20, p. 257-264 (1947);C. A. 42, 2735e.

- 29 -

29. Austin, L. W., and Hicks, J. C. Refractory bonding material. U. S.patent 2,628,915, Feb. 17, 1953 (to Kaiser Aluminum and Chemical Corp.);C. A. 47, 6108h.

30. Zhuravlfiv, V. F., and Zhitomirskaya, V. I. Binding properties of crystalhydrates of the sulfate type. J. Applied Chem. U.S.S.R. , v. 23,p. 115-119 (1950) (English translation); C. A. 45, 3141c.

31. Goeddel, W. V., and Simnad, K. T. Metal bonded carbon bodies.U. S. patent 3,001,238, appl. Dec. 31, 1958 (to U. S. Atomic EnergyComm.); C. A. 56, 7035i.

32. Engel, W. J. Bonding investigation of titanium carbide with variouselements. Natl. Advisory Comm. Aeronaut., Tech. Note 2187, 15 p. (1950);C. A. 45, 1931c.

33. Mendelsohn, L. I. Molded magnet and magnetic material. U. S. patent2,724,174, Nov. 22, 1955 (to General Electric Co.); C. A. 50, 3678f.

34. Cline, C. F. Carbide-bonded graphite bodies. U. S. patent 3,007,805,appl. Aug. 22, 1957 (to Carborundum Co.); C. A. 56, 6930b.

35. Romanov, V. D. Hard alloys prepared by the metal-ceramic method.U.S.S.R. patent 82,155, Nov. 22, 1958; C. A. 53, 16910b.

36. Societe d'etude et de relisation d'outillage diamante. Agglomerationof diamond powder. French patent 1,243,527, Jan. 16, 1961; C. A. 55,203 70i.

37. Redfarn, C. A. Binders for abrasives. German patent 1,042,451,Oct. 30, 1958; C. A. 55, 4056g.

38. Thompson, J. S. Bonding materials. U. S. patent 2,702,425,

Feb. 22, 1955 (to Parker Rust Proof Co.); C. A. 49, 10598c.

39. Bruk-LeVinson, T. L. Rational methods for the neutralization of

sulfate-containing waste pickling liquors. Materialy Soveshchaniya po

Voprosam Ochistki Prom, i Stochnykh Vod, Moscow, 1955, p. 170-175

(pub. 1957); C. A. 53, 22642h.

40. Bendryshev, A. P., and Shapiro, A. D. Binder for abrasive goods.

U.S.S.R. patent 47,897, July 31, 1936; C. A. 33, 3554s .

41. Metzger, L. H. Bonding adhesives for abrasives. U. S. patent 2,376,163,

May 15, 1945 (to Industrial Abrasive Inc.); C. A. 39, 34 123 .

42. Dietrich, Alfred. Pellets from finely ground materials, especially ores.

German patent 969,626, July 3, 1958 (to Duisburger Kupferhutte);

C. A. 54, 6492d.

43. Bechtold, M. F., and Snyder, 0. E. Chemical processes and composition.

U. S. patent 2,574,902, Nov. 13, 1951 (to E. I. du Pont de Nemours

and Co.); C. A, 46, 1669h.

44. Bugosh, John. "Ludox" (colloidal silica) as a binder. Private

communication, June 25, 1964.

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45. Evers, Dietrich. Granular lead oxides. German patent 1,013,273,Aug. 8, 1957 (to Accumulatoren-Fabrik Akt.-Ges.); C. A. 54, 8006h.

46. White, E. S., Singer, Norbert, and Hays, J. W. Bonding of carbon bodies.German patent 1,077,132, Mar. 3, 1960 (to Morgan Crucible Co., Ltd.);

C. A. 55, 23955i,

47. Sugita, Toranosuke. Molded articles of artificial graphite. Japanesepatent 173,957, Oct. 24, 1946 (to Hidachi Mfg. Co.); C. A. 46, 2207b.

48. Reppert, R. L. v. Granular superphosphates . German patent 863,947,Jan. 22, 1953 (to Chemische Werke Albert); C. A. 52, 15813d.

49. Serra, E. B, Conglutinative agents. Spanish patent 231,624, Feb, 20,

1957; C. A. 51, 15900i.

50. Iwata, Yoshimichi. Coagulating agent for earth and sand. Japanesepatent 2285(1958), April 5; C. A. 53, 3652e.

51. Cohen, Harry, Agglomeration of iron ores in the blast furnace.U. S. patent 2,771,355, Nov. 20, 1956; C. A. 51, 2514i.

52. Polle, Wilhelm. Fuel briquets. German patent 1,057,067, May 14, 1959;C. A. 55, 8822h.

53. Kerla, Hans. Binding materials. U. S. patent 2,855,318, Oct. 7, 1958;C. A. 53, 1666a.

54. Klause, K. Wollastonite bodies of high compressive strength for abrasivewheel binders and similar purposes. Keram. Z., v. 8, p. 455-457 (1956);C. A. 52, 8491i.

55. Zhuravlev, V. F., and Zhitomirskaya, V. I. Binding properties of crystalhydrates of the sulfate type. J. Applied Chem. U.S.S.R., v. 23,

p. 237-239 (1950) (English translation); C. A. 45, 6948d.

56. Kaufmann, Waldemar, and Buchmann, Annie, Alginic acid binder for fuelbriquets. German patent 938,899, Feb. 9, 1956 (to Farbwerke HoechstA.-G. vorm. Meister Lucius und Bruning); C, A. 52, 150311.

57. Miischenborn, Walter. Briquetting of fine-grained substances. Germanpatent 810,153, Aug. 6, 1951; C. A. 47, 8350b.

58. McKee, J. H. Solid materials consisting of aggregated solid particles.U. S. patent 2,652,318, Sept. 15, 1953 (to C.U.R.A. Patents, Ltd.);C. A. 48, 4196e.

59. Nilus, S. G., and Shapiro, M. D. Production and utilization of ASK(anthracene -sulfur binder) (for briquets). Trudy Dnepropetr.Khim-Tekhnol. Inst., 1959, no. 12, pt. 1, p. 163-170; C. A. 57, 3713h.

60. Meyerhans , Konrad, Adhesive and molding resins on the basis of Araldite.Kunststoffe, v. 41, p. 365-373 (1951); C. A. 46, 2841h.

61. Meyerhans, Konrad. Araldite as a binder and as a casting resin.Kunststoffe, v. 41, p. 457-462 (1951); C. A. 46, 3793b,

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62. Bonnier, J. C, Lusinchi, J., Laly, m. , and Waes, M. Use of petroleumasphalt in the agglomeration of coal fines. Rev. ind. mine'rale, v. 40,p. 581-602 (1958); C. A. 53, 4697h.

63. Vaquin, J. C. Agglomerating tar. French patent 1,177,202, Apr. 22,1959 (to Compagnie de raffinage Shell-Berre) ; C. A. 54, 25783h.

64. Gutsalyuk, V. G., Rafikov, S. R., and Bayarstanova, Zh. Zh. Plasticasphalt by oxidation of extracts. Izvest. Akad. Nauk Kazakh. S.S.R.,Ser. Khim., 1959, no. 2, p. 72-78; C. A. 53, 17489d.

65. Zvenigorodskii, G. Z., Brekhunenko, F. F., and Krokhin, V. N. Thereplacement of coal pitch in coal briquet production by the oxidizedheavy residues of processed petroleum. Voprosy Obogashch. i Briketir.Uglei, Vsesoyuz. Nauch. Issledovatel. Ugol. Inst., Sbornik 9,p. 111-134 (1953); C. A. 50, 6772i.

66. Hassard, William. Bituminous compositions. British patent 476,173,Dec. 2, 1937; C. A. 32, 3932 6 .

67. Mollring, G. B. Liquid bituminous binder. U. S. patents 2,783,162 and2,783,163, Feb. 26, 1957; C. A. 51, 6976c.

68. Hemmer, Lucien. Improving the adhesivity of bituminous compositionssuch as those used for binders in road construction. U. S. patent2,342,681, Feb. 29, 1944 (to Standard Catalytic Co.); C. A. 38, 4770 5

.

69. Holmes, August. Asphalt binders for moist aggregates. U. S. patent2,375,653, May 8, 1945 (to Standard Catalytic Co.); C. A. 39, 3646 7.

70. Mitchell, L. J., and Sommer, H. J. Asphalt bituminous bondingcomposition. 0. S. patent 2,534,828, Dec. 19, 1950 (to Shell DevelopmentCo.); C. A. 45, 2647a.

71. Kaufler, Felix, and Schmitz, H. P. Stable asphalt solutions suitablefor use in coating, binding, or impregnating various materials.

U. S. patent 2,102,957, Dec. 21, 1937; C. A. 32, 1445 5.

72. Dimitriu, Mikail. Practical and theoretical basis of the problem of

adhesion of bituminous binders to mineral aggregates, Inst. geol.

Romaniei, Studii tech. econ., ser. B, no. 25, 149 p. (1946) (French

summary); C. A. 42, 8438a.

73. Zakar, Pal, and Toth, Joseph. Briquets with petroleum residues

(bitumens) as binders. Brennstoff-Chem. , v. 39, p. 373-379 (1959);

C. A. 53, 5633i.

74. Zakar, Pal, and Mozes, Gyula. Petroleum bitumen for briquet ting.

Bitumen, Teere, Asphalte, Peche, v. 9, p. 275-280 (1958); C. A. 53,

1693h.

75. Siegl, Adolf, Eisenhut, Franz, and Gobiet, Viktor. Bitumen for

briquetting of ores. German patent 1,032,547, June 19, 1958 (to

Gelsenkirchener Bergwerks A.-G.); C. A. 54, 17222g.

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76. Popov, V. L. A study of shale bitumens as bonding agents in thebriquetting of coals. Trudy Inst. Goryuch. Iskopaem., Akad. NaukS.S.S.R., v. 12, p. 115-123 (1961); C. A. 55, 20387d.

77. Khotuntsev, L. L. , Popov, V. L. , and Volkov, G. M. New kind of bindersfor briquetting of coal fines. Ugol 1

, v. 35, no. 4, p. 51-55 (i960);C. A. 55, 3036a.

78. Levin, I. S., Gurevich, B. S., and Zvenigorodskii, G. Z. Use ofbitumen-water emulsions in the briquetting of coal fines. Trudy Gos.Proektno-Konstrukt. Nauchn.-Issled. Inst, po Obogashch. i Briketir.Uglei, 1961, no. 16, p. 62-69; C. A. 57, 11463h.

79. Mertens, E, W. Quick-breaking bituminous emulsions having increasedadhesion to mineral aggregates. U. S. patent 2,862,831, Dec. 2, 1958(to California Research Corp.); C. A. 53, 5634b.

80. Mertens, E. W. , and McCoy, P. E. Quick-breaking bituminous emulsions.U. S. patent 2,862,830, Dec. 2, 1958 (to California Research Corp.);C. A. 53, 5633d.

81. Boneysteele, P. L. , and McKercher, M. L. Bituminous emulsions suitablefor use as coatings, binders, etc. U. S, patent 2,135,866, Nov. 8,

1938; C. A. 33, 14682 .

82. Woodall-Duckham (1920) Ltd. Covering mineral aggregates with bituminousbinders. French patent 850,907, Dec. 29, 1939; C. A. 36, 21119 .

83. Ariano, Raffaele. Adhesion of bitumen to rock materials. Ricerchee studi ist. sper. stradale C.T.I, e R.A.C.I., v. 5, p. 111-121 (1941);C. A. 42, 734b.

84. Lhorty, M. L. Improving the adhesion of bituminous and other hydro-carbon binders, German patent 1,103,223, appl. Feb. 15, 1955 (to

Bataafse Petroleum Maatschappij N. V.); C. A. 56, 6265e.

85. Holmes, August, and Hemmer, Lucien. Improving the adherence of bitumen.French patent 847,829, Oct. 17, 1939 (to Standard franchise des pe'troles);

C. A. 35, 60293 .

86. Hemmer, Lucien, and Jouandet, C. Binders of improved adhesiveness.French patent 1,007,202, May 5, 1952 (to Standard franchise des pe'troles);

C. A. 51, 10893g.

87. Hemmer, Lucien, Flavigny, R., and Leveuf, M. Binders of improvedadhesiveness. French patent 1,007,203, May 5, 1952 (to Standardfranqaise des pe'troles); C. A. 51, 10893h.

88. Friedrich, Paul. Binder for briquetting coal and coke. German patent732,413, Feb. 4, 1943; C. A. 38, 8527 .

89. Klimkova, A. F. High-melting bituminous compositions, Korroziya i

Borba s Nei, 1940, no. 3, p. 44-50; C. A. 37, 423

7

1.

-sa-

go. Havestadt, Ludwig. Bitumens and bituminous binders for buildingmaterials. German patent 1,071,569, appl. Nov. 12, 1956 (to Th.Goldsmidt A.-G.); C. A. 56, 6267c.

91. Hemmer, Lucien. Adhesive bitumens. French patent 826,788,Apr. 8, 1938 (to Standard francaise des pe'troles); C. A. 32, 81311 .

92. Halbach, Karl. Binding material suitable for uniform slow setting.U. S. patent 2,210,367, Aug. 6, 1940; C. A. 35, 2964 .

93. Shea, F. L. , Jr., and Juel, L, H. Use of organic nitro compounds inbinders for making carbon bodies. U. S. patent 2,527,596 (to GreatLakes Carbon Corp.); C. A. 45, 336d.

94. Havestadt, Ludwig, and Arens, Hugo. Improvement of adhesiveness ofbituminous binding agents and coating compounds. German patent 800,685,Nov. 27, 1950 (to Th. Goldschmidfc A.-G., Chemische Fabrieken); C. A. 45,3142e.

95. Woodell, C. C. , Van Nimwegen, Garrett, and Hager, E. T. Abrasive

article. U. S. patent 2,577,060, Dec. 4, 1961 (to Carborundum Co.);

C. A. 46, 2260a.

96. Lolkema, Jan, and Kool, C. M. H. Insoluble layers from carbohydrates.

U. S. patent 2,541,773, Feb. 13, 1951 (to N. V. W. A. Scholten's

Chemische Fabrieken); C. A. 45, 4954c.

97. Lukaszczyk, A. Carubin and Guaran as binders and thickeners.

Textil -Rundschau, v. 15, p. 130-134 (1960); C. A. 54, 13701a.

98. Petrovich, G. G. Cement for abrasives. U.S.S.R. patent 69,412,

Oct. 31, 1947; C. A. 43, 9408h.

99. Mayer, Erwin, and Bolin, E. A. F. Binding agents, German

patent 928,725, June 10, 1955 (to Uddeholms Aktiebolag); C. A. 52, 5888b.

100. Dryden, I. G. C, and McKee, J. H. Binder for solid particles. U. S.

patent 2,652,354, Sept. 15, 1953 (to C.U.R.A. Patents, Ltd.); C. A. 48,

4196g.

101. Taits, E. M. , Bronovets , T. M. , and Andreeva, I. A. Binder,

especially for briquetting coal. U.S.S.R. patent 150,483, Oct. 11, 1962;

C. A. 58, 8825b.

102. Reichhold Chemie A.-G. Air-setting binders for foundry sand. British

patent 911,173, Nov. 21, 1962; C. A. 58, 3190d.

. Pietsch, Helmut. Curing epoxyesters with polycyclic aromatic amines.

German patent 1,070,372, Dec. 3, 1959 (to Henkel and Cie., G. m. b. H.);103

C. A. 55, 10967g.

104. Doenhoff, Carl v. Adhesives for abrasives. German patent 1,135,168,

Aug. 23, 1962 (to The Carborundum Co.); C. A. 58, 638e.

105. Hart, D. P. Bonding composition. U. S. patent 2,919,255, Dec. 29, 1959

(to Pittsburgh Plate Glass Co.); C. A. 54, 12615h.

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106, Treat, L. H., and Shaffer, R. C« Aqueous she 11-molding compositions formetals from maleic acid, furfuryl alcohol, and urea, U, S, patent2,999,829, appl. June 25, 1954; C. A. 56, 596g.

107. Lesser, M. A, Glycerol in ceramics and enamels, Ceram, Age, v, 49,p. 300-302 (1947); C. A. 42, 8434e.

108, Robie, N. P., and Mahlman, 0. L, Abrasive articles. U. S. patent2,369,689, Feb. 20, 1945 (to The Carborundum Co.); C. A. 40, 6943 .

109. Zhikharev, S. A. Binders for coal briquet3. U.3.S.R. patent 64,461,Apr. 30, 1945; C. A. 40, 52282 .

1X0. Volkov, G. M. The role of humic acids in the briquetting of solidfuels. laves t. Akad. Nauk S.S.S.R., Otdel Tekh. Nauk, Met. i Toplivo,1959, no. 4, p. 251-253; C. A. 55, 16957e.

111, Badische Anilin and Soda Fabrik. (Trihydroxyalkyl)dialkylenetriamines,their hydrohalide salts, and condensation products. British patent680,688, Oct. 8, 1952; C. A. 49, 2486h.

112. Benko, Joseph, Measurement of the relative molecular weight oflignosulfonates by diffusion. III, The effect of molecular size onsurface -active and other properties of lignosulfonates, Tappi, v. 44,

p. 849-854 (1961); C, A. 56, 13133b.

113. Kovats , Lajos. Binder for coal briquets. Hungarian patent 121,424,Sept. 1, 1939; C. A. 34, 1466".

114, Carbofor. Cement for wood charcoal. French patent 861,930, Feb. 21,

1941; C. A. 42, 6092b.

115* Carabasse, Joseph, Choquereau, Hector, and Chaix, Raymond. Coalbriquets. French patent 1,177,359, Apr. 23, 1959 (to Houilleres du

Bassin-du-Nord et du Pas-de-Calais); C. A, 55, 949c.

116. Yamada, Keihiko. Molded products from high-density carbon and graphite.Japanese patent 3959(1961) (to Tokai Electrode Mfg. Co., Ltd.);

C. A. 56, 3746i.

117. Hessel, F. A., and Rust, J. B. Abrasive bodies. U. S, patent

2,559,122, July 3, 1951 (to Montclair Research Corp.); C. A. 45, 8733a.

118. Gel'ts, Vo E., and Adamskaya, R, I. Binding material. U.S.S.R,patent 110,491, June 25, 1958; C. A. 52, 14225c.

119. Vichnevetzky, Leon, and Manson, Izak. Hydrocarbon binder. Frenchpatent 843,063, June 26, 1939; C. A. 34, 63909 .

120. Champagnat, Alfred, Mo let, Louis, and Stern, Robert. Petroleum pitchfor coal-briquet manufacture^ British patent 876,191, appl. Feb. 29,

1960 (to British Petroleum Co., Ltd.); C. A. 56, 5028b.

121. Dunkel, W. L, , McAteer, J, H., and Stewart, Joseph, Binders for carbonelectrodes from petroleum, U, S. patent 2,772,219, Nov. 27, 1956 (toEsso Research and Eng, Co.); C» A. 51, 4690h.

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122. Laboure, Maurice, and Malzac, Albert. Carbonaceous binders forsolid fuels. French patent 1,000,699, Feb. 14, 1952; C. A. 513117e. '

/ •123. Societe industrielle de produits chimiques. Bituminous binders. French

patent 1,002,247, Mar. 4, 1952; C. A. 51, 4606i.

124. Onozawa, Tstsugoro. Molding agent for solid fuel. Japanese patent3680, May 19, 1956; C. A. 51, 10875f.

125. Evans, J. I. Coal briquets. British patent 881,878, appl. Mar. 18,1959 (to Monsanto Chemicals, Ltd.); C. A. 56, 7620i.

126. Webber, C. S. Adhesives for coated abrasives. U. S. patent 2,876,087,Mar. 3, 1959 (to Norton Co.); C. A. 53, 10852g.

127. Aktiebolaget Hoganasmetoder. Modified resin binders for siliceousmaterials. British patent 876,033, appl. Oct. 1, 1958; C. A. 56, 4974i.

128. Kazakova, K. S., Brodskii, G. Sh., and Rabits, S. M. Abrasives.U.S.S.R. patent 123,056, Oct. 10, 1959; C. A. 54, 8024c.

129. Crowley, H. L. Binder for agglomeration of finely divided materials.U. S. patent 2,775,566, Dec. 25, 1956 (to Aerovox); C. A. 51, 4606h.

130. Redfarn, C. A. Abrasive articles, U. S. patent 2,897,074,July 28, 1959; C. A. 53, 20742d.

131. Parkes, D. W. Tar binders. British patent 538,308, July 29, 1941(to Midland Tar Distillers, Ltd.); C. A. 36, 1470 5

.

132. Stepanenko, M. A., Matusyak, N. I., and Gogoleva, T. Ya. Pitchdistillate as a bonding material for briquetting coal. Koks i Khim.,1957, no. 1, p. 32-35; C. A. 51, 8408e.

133. Eisenhut, Franz, Gobiet, Viktor, and Siegl, Adolf. Binders for

briquetting coal. German patent 957,753, Feb. 7, 1957 (to

Gelsenkirchener Bergwerks Akt.-Ges.); C. A. 53, 1071Qf.

134. Eisenhut, Franz, Gobiet, Viktor, and Siegl, Adolf. Binders for

briquetting coal. German patent 958,554, Feb. 21, 1957 (to

Gelsenkirchener Bergwerks Akt.-Ges.); C. A. 53, 107l0g.

135. Eisenhut, Franz, Gobiet, Viktor, and Siegl, Adolf. Binder for

briquetting solid fuels. German patent 1,011,851, July 11, 1957 (to

Gelsenkirchener Bergwerks Akt.-Ges.); C. A. 54, 8036g.

136. Eisenberg, Albrecht, Eisenhut, Franz, Gobiet, Viktor, and Siegl,

Adolf. Tar-pitch melts as binders. German patent 1,025,829,

Mar. 13, 1958 (to Gelsenkirchener Bergwerks Akt.-Ges.); C. A. 54,

11445h.

137. Eisenhut, Franz, Gobiet, Viktor, and Siegl, Adolf. Binder dispersion

for the briquetting of fuels. German patent 1,007,736, May 9, 1957

(to Gelsenkirchener Bergwerks Akt.-Ges.); C. A. 54, 9257e.

- 36 -

138. Tcarev, M. N. , Shpakhler, A. G., Korchagin, L. V., Pluzhnik, V. I.,

Zel'din, B. B. , and Bul'shtein, B. M. Pitch and pitch distillates asbinding agents for briquetting coal fines. Koks i Khim., 1959, no. 9,

p. 45-49; C. A. 54, 7107i.

139. Golovanov, N. G. Coal-tar residues as binders in the briquetting ofcoal fines. Trudy Nauch.-Issledovatel. Inst. Mestn, i Toplivn. Prom.,1958, no. 12, p. 108-116; C. A. 55, 5913g.

140. Brandes, C E. Briquets. German patent 807,275, Sept. 10, 1951;C. A. 46, 8832e.

141. Wiszmiowski, Kazimierz. Pitch for briquetting. Koks, Sraola, Gaz,v. 2, p. 77-81 (1957) (English summary); C. A. 51, 18552i.

142. Frishmelt, Erich. Microscopic observation of pitch in hard-coalbriquets. Brennstoff-Chem. , v. 38, p. 97-102 (1957); C. A. 51, 10029h.

143. McNeil, D. , and Wood, L. J. Coal-tar pitch as an electrode binder.Ind. Carbon and Graphite Papers Conf., London, 1957, p. 162-172(pub, 1958); C. A. 53, 10709b „

144. Tadenuma, Hachiro. Effective components as binding material for carbonpowder in coal-tar pitch, J. Chem. Soc. Japan, Ind. Chem. Sec, v. 56,

p. 516-519 (1953); C. A. 48, 11759c.

145. Croy, Friedrich. Electrode pitch. U. S. patent 2,864,760, Dec. 15,

1958; C. A. 53, 7563a.

146. Marukawa, Hideo, Briquet binder. Japanese patent 177,015, Nov, 26,

1948; C. A. 45, 5392f.

147. Dolkart, F. Z. The properties of refractories of calcined dolomitewith a pitch binder. Ogneupory, v. 26, p. 329-335 (1961); C. A. 55,

27825g.

148. Gemmi, Angiolo. Bonding carbon- or graphite -molded bodies together orwith metal parts, German patent 1,107,578, appl. Nov. 21, 1958 (to

Elettrocarbonium S. p. A. Mailand); C. A. 56, 7620h.

149. Bauerfeld, Franz, and Richter, Friedrich. Binders from coal tar pitch.

German patent 968,357, Feb. 6, 1958 (to Gesell, fur Teerverwertungm. b. H.); C. A. 54, 9259f.

150. Rodman, Hugh, Jr. Activated carbon. U. S. patent 2,648,637, Aug. 11,

1953 (to Rodman Chemical Co.); C. A. 47, 10828c.

151. Grosskinsky, Otto, Meyer, Hermann, and Umbach, Helmut. Briquets.German patent 807,513, June 28, 1951 (to Bergwerksverband zur

Verwertung von Schutzrechten der Kohlentechnik G. m. b. H.);C. A. 46, 8832e.

152. Matsunami, Hidetoshi. Binder for solid fuel. Japanese patent6138(1954), Sept. 25; C. A. 50, 555a.

- 37 -

153. Swift, A. M. Polyacrylamide — a new synthetic water-soluble gum.Tappi, v. 40, no. 9, p. 224A-227A (1957); C. A. 52, 6837f.

154. Morton, J. S. Abrasive compositions. U. S. patent 2,980,524, Apr. 18,1961 (Engis Equipment Co.); C. A. 55, 27836h.

155. Hatte, P. L. M. Magnetic cores. French patent 1,003,831, Mar. 24,1952; C. A. 51, 6912f.

156. Silver, R. P. Polyester resins in aqueous solutions. U. S. patent2,884,394, Apr. 28, 1959 (to Hercules Powder Co.); C. A. 53, 136621.

157. Stamicarbon N. V. Fuel briquets. Netherlands patent 99,175, appl.Feb. 20, 1959; C. A. 56, 1692h.

158. Reuter, F. G. Elastic binders for abrasive articles. German patent1,010,732, June 19, 1957 (to Lemfb'rder Metallwaren G. m. b. H.);C. A. 53, 22816a,

159. Ford, J. G. Bonding composition for magnetic metal. U. S. patent2,372,074, Mar. 20, 1945 (to Westinghouse Electric Corp.); C. A. 39,5562 3 .

160. Ariano, Raffaele. Binder from prickly pears. Ricerche e studl ist.sper. stradale C.T.I, e R.A.C.I. , v. 6, p. 18-19 (1942); C. A. 42,734c.

161. Dehler, H. Strength and economy of compacted magnets having asynthetic binder. Elektrotech. Z. , v. 65, p. 93-95 (1944); C. A. 41,6179h.

162. Kurth, Herbert, and Oelenheinz, Theodor. Binder for cementing fuelbriquets. German patent 718,469, Feb. 19, 1942; C. A. 38, 2478

2.

163. Wille, Hans, Jellinek, Karl, and Stanke, Helmut. Water-resistantbinders for abrasives. German patent 1,116,392, appl. Dec. 7, 1957(to Gesellschaft fur Teerverwertung m. b. H.); C. A. 56, 4392b.

164. Gadolla, Eugen, and Pruscha, Hans. Fuel briquets. Austrian patent

179,771, Oct. 11, 1954; C. A. 48, 14164h.

165. Zvenigorodskii, G. Z., and Antonova, T. N. Utilization of shales in

coal briquetting. Sbornik Inform, po Gbogashch. i Briketir. Uglei, 1957,no. 3, p. 23-28; C. A. 55, 4921g.

166. Goepfert, G. J., and Spilsbury, W. A. Shellac -bonded abrasive

articles. U. S. patent 2,709,647, May 31, 1955 (to Carborundum Co.);

C. A. 49, 14290e.

167. Dohmen, Heinrich. Air hardening material from starch and cellulose

ethers. U. S. patent 2,835,610, May 20, 1958 (to N. V. Eldeka);

C. A. 52, 19199c.

168. Briko N. V. Binder for fuel briquets. Dutch patent 97,828, May 15,

1961; C. A. 55, 20393h.

- 38 -

169. Dohraen, Heinrich. Briquet binder. U. S. patent 2,890,945, June 16,

1959 (to N. V. Briko); C. A. 53, 22342b.

170. Squire, L. R. L. Binders for aggregates such as fuel briquets.British patent 502,619, Mar. 22, 1939; C. A. 33, 7994 6 .

171. Erickson, J. A. Solid fuel briquets. British patent 566,001, Dec. 8,1944; C. A. 40, 5549

1.

172. Mo'ller, F. A., and Lolkema, Jan 4 Starch compositions capable offorming water-soluble derivatives. U. S. patent 2,451,686, Oct. 19,1948 (N. V. W. A. 'Scholten's Chemiache Fabrieken); C. A. 43, 1590d.

173. Moes, G., and Zijderveld, A. H„ Application of a water-insoluble layeron a support. Belgian patent 613,242, Feb. 15, 1962 (to N. V. W. A.

Scholten's Chemische Fabrieken); C, A. 53, 1625b.

174. Lolkema, Jan, and van der Meer, W, A. Starch solutions. U. S. patent2,575,423, Nov. 20, 1961 (to N. V. W. A. Scholten's ChemischeFabrieken); C. A. 46, 2324d.

175. Weithbner, Richard, and Brockhausen, Karl, Preparing copolymers of a

vinyl monomer of the styrene group and drying or semi-drying oil.

German patent 929,448, June 27, 1955 (to Glasurit-Werke, M. WinkelmannA.-G.); G« A. 52, 6849d.

176. Bartke, W.tlhelm. Briquetting the dust of lignite briquets by means of

sulfite waste liquor as a binder. East German patent 18,372, Apr. 1,

1960; C. A. 55, 10852f.

177* Ledent, P., and Marcourt, M. Low-temperature carbonization of coalbriquets containing sulfite liquor or cassava flour as binder. Inst,

natl. ind. charbonniere, Bull. tech. Houille et derives, no. 20,

p. 579-588 (1960); C. A. 55, 2059d.

178. Reznik, L. Ya. Binder for briquetting small coal. U.S.S.R. patent

93,879, July 20, 1962; C. A. 58, 2300g.

179. Eisenhut, Franz, Gobiet, Viktor, and Siegl, Adolf. Binders for briquets.German patent 1,017,592, Oct. 17, 1957 (to Gelsenkirchener BergwerksAkt.-Ges.); C. A. 54, 11445tu

180. Douglas, J. F. Adhesion between binders and individual rock-formingminerals. J. Soc. Chem. Ind., v. 65, p. 377-379 (1946); C. A. 41,2S71a.

181. Levin, I. S., and Kharlampovich, G. D. New types of bonding agentsfor briquetting fuels. Ugol 1

, v. 37, no. 9, p. 48-52 (1962); C. A. 58,384c.

182. Nyvlt, N. Substitute binders for briquets from anthracite powder.Paliva, v. 37, p. 375-380 (1957); C. A. 52, 8505e.

J83. Lahr, Georg. Oxidizing additions to binder agents for coal briquets.German patent 967,066, Sept. 26, 1957 (to Vereinigte Aluminum-WerkeAkt.-Ges.); C. A. 54, 6093i.

- 39 -

184. Gandusio, G. , and Strocchi, P. M. Tar and pitch as binders. Riv.combustibili, v. 12, p. 562-580 (1958); C. A. 53, 4712g.

185. Nadziakiewicz, J., and Rulikowski, G. Ways of reducing theconsumption of binding materials in the briquetting of semicoke . Koks

,

Smola, Gaz, v. 3, no. 5, p. 180-184 (1958); C. A. 55, 20601.

186. Wataru, Shinjiro, and Yuiki, Nakaharu. Binders for fuel briquets.Japanese patent 2479(1958), Apr. 10 (to Bureau of Industrial Technics);C. A. 53, 3665h.

187. Lacau, R. J. Adhesive binder. French patent 1,006,740, Apr. 28, 1952;

C. A. 51, 9132e.

188. Sarkar, A. K. Physicochemical study of the action of lime on coal tar.

Kolloid Z., v. 132, p. 24-30 (1953)(in English); C. A. 48, 346f.

189. Shvarts, I. D. Obtaining compressed calcium carbide from carbide dust.

J. Chem. Ind. (U.S.S.R.), v. 18, no. 7, p. 17-23 (1941); C. A. 38,

24735

.

190. Uvarov, I. P., Gordon, L. V., and Gusakov, V. N. Wood tar as adhesive

for charcoal briquets, Gidroliz. i Lesokhim. Prom., v. 10, no. 4,

p. 10-11 (1957); C. A. 51, 15123a.

191. Nagarajan, V., and Thampy, R. T. Bonding agents for abrasive articles.

Research Ind. (New Delhi), v. 6, p. 311-313 (1961); C. A. 56, 2570i.

192. Rupprecht, W. E. F. Binders for abrasives. U. S. patent 2,965,464,

Dec. 20, 1960 (to Dow Chemical Co.); C. A. 55, 11795b.

193* The Carborundum Co. Abrasives. French patent 815,704, July 21, 1937;

C. A. 32, 1890*.

194, Sauvage, E. J. A. Binder for powdered, granular, or fibrous substances.

Belgian patent 558,266, June 29, 1957; C. A. 53, 22620a.

195. Finger, G. C, , Risser, H. E., and Bradbury, J. C. Illinois fluorspar.

Illinois Geol. Surv. Circ. 296, p. 26 (1960).

- 1+0 -

INDEX

Abrasives 4,5,6,7,8,10,11)- ,15,

16,1TA9,21,22,23,26Absorbents 6

Absorption oils 20

Acetaldehyde 18,22Acetic acid l8,2J,2UAcetone 9Acids, aromatic 15Acids, hydroxy 17,26Acids, naphthenic Ik

Acids, polybasic unsaturated 16Acrylamide, poly- 21Acrylic acid l6Activated carbon (See carbon,

activated)Adhesion 12,25Aggregates, mineral or rock 12,

13,1^25Alcohols, polyhydric 10Aldehydes 2k

Alginic acid 11

Alkali cellulose (See cellulose,alkali)

Alkoxysilicons 1^,17Alkyl sulfates . 13Alloys 7Alnico 7Alpha . component 20

Alumina (See also aluminumoxide, boehmite, corundum) 3,

if, 5,8,22Alumina cement 8

Aluminates 3Aluminum 3,7Aluminum borate k

Aluminum humate 16Aluminum hydroxide 5

Aluminum ion 16Aluminum nitride 3Aluminum oxide (See also

alumina, boehmite) 4,8, 18Aluminum phosphate k

Aluminum sulfate 15, 18

Amides 13Amides, poly- 15,22Amines k, 11,13,14,15

Amine s , hydroxy-AmmoniaAmmonium acetateAmmonium chlorideAmmonium fluorideAmmonium humateAmmonium hydroxideAmmonium ion

16

9,1818

8,16k

1616,18

16Ammonium peroxydi sulfate 25Anhydrite (See calcium sulfate)Anthracene 11,19,20Anthracene oil 11,19,21,25Anthracite (See coal, anthra-

cite)Antimony aluminate 3Araldite

.

11Argon 9Aromatic acids (See acids, aro-

matic )

Asbestos 3,5,26Ash, fly 11Asphalt 11,12Asphaltite Ik

Attapulgite k

Augite 25

Barium hydroxide 2k

Baymal 3Benzenesulfonyl chloride, nitro-

21Benzidine 15Benzoyl peroxide 16Benzyl alcohol 25Beryllium 7Beryllium oxide k

Beta component 20

Biotite 25Bis ( 2 - chloroethyl) formal poly-

sulfide (See sulfides, poly-^2,2-Bis(4-hydroxy-3-allylphenyl)-

propane (See phenol, 4,4'--

isopropylidenebis -2- allyl-)Bitumens (See also pyrobitumens)

11,12,13,1^,16,17, 18Bitumen, shale 23Boehmite 3

41 -

Boleka oil (See oil, Boleka)Borate glass (See glass,

borate)Boric acid 8,19,22Boron 7Boron aluminate 4

Boron carbide 4,7Boron oxide, B2 3 4 ,8

Borosilicates 4Bricks, fire ^,5,6Bricks, lead- containing 26Briquets, fuel 6,10,11,12,13,

15,16,17,18,19,20,21,22,23,24,25,26

Brown coal (See coal, brown)1,3-Butadiene 14,22,261,4-Butanediol 22

Butene 22tert -Butyl peroxide 24

Butyl stearate 19

Calcium aluminate 5

Calcium carbide 26Calcium carbonate (See also

limestone) 8

Calcium chloride 9Calcium chromite 4

Calcium fluoride 4,9Calcium germanate 4

Calcium humate 16Calcium hydroxide 6,15Calcium ion 16Calcium oxide (See also lime) 4,

5,6,14Calcium phenolates 14

Calcium phosphate (See super-phosphates)

Calcium silicate (See wollas-tonite)

Calcium stearate 19

Calcium sulfate (See alsogypsum) 5,8

Carbides (See also names of

various metals) 7,9Carbohydrates (See also cellu-

lose) galactose) molasses;polysaccharides; starch;

sugar

)

14 , 18

Carbon 9, 14, 17, 18,21,25Carbon, activated 21,25Carbonyls (See metal carbonyls,

and various metals, e.g.., iron)Carborundum (See silicon car-

bide)

Carbowax 19Carnauba wax 9Carob bean (locust bean) gum 14Carubin 14Casein 12, 14Cassava flour 15,17,24Castor oil, sulfonated 8

Catalysts 5,6,17,18Cellulose 21Cellulose, alkali 11Cellulose, carboxymethyl ether,

sodium salt (See sodium car-boxymethyl cellulose)

Cellulose derivatives 15,18,21Cement (See also portland

cement) 5

Cement, alumina (See aluminacement

)

Ceramic materials 11, 14, 15, 16Ceresin 3Chalk 5

Charcoal 11,17,18,26o-Chlorophenol (See phenol,

o-chloro-)Chloroprene 14

Chromium 7Chromium aluminate 3Chromium carbide 7Chromium chloride, CrCl3 21Chromium compounds 5,26Chromium ore 5

Chromium oxide, Cr2 3 4

Chromium silicide 9Citric acid 10

Clay 4,5,20Coal 10,11,12,13,14,15,16.17,

18,19,20,21,22,23,24,25,26Coal, anthracite 25

Coal, brown (See also lignite)

16,20,23,25Coal, hydrogenation products

of 15

Coalite 6

Cobalt 7,15Coke 11,14

Coke, petroleum 11

Coke, pitch 11,20

Collodion 9Colloid, protective 21

Copper 6,8

Corundum 4,8

Creosote oil 14

Cresylic acid (cresols) 22

- 42

Cyclohexane, 1,2,3,4,5,6-hexa-chloro- 9

Dextrin 23

Diamond 4,6,8,21Diatomaceous earth (See also

kieselguhr) 5

Dichloroethane (See ethane, di-chloro-)

Diglycidyl terephthalate (Seeterephthalic acid, diglycidylester)

Dilinoleic acid (See linoleicacid, dimer)

Dinas 6

Dipentene 24

Dolomite 6,21Drying oils (See oils, drying)

Electric charge 3

Electric furnace (See furnace,

electric)Electrodes (carbon) 9,14,18,20,21Emulsions 13,20,21,22,25,26Epichlorohydrin 15Epoxy resins (See also Araldite)

11,15Esters 12,14,19,22,24Esters, poly- 22

Ethane, dichloro- .8

Ethane, tetrachloro- 8

Ethanol 22Ethene (See ethylene)Ether, allyl 22

Ethers 12, 14

Ethylene 22Ethylenediamine 15Ethylene, 1,1-dichloro- (See

vinylidene chloride)

Ethylene glycol 15,22Ethylene oxide 21

Ethylene oxide polymers 21

Ferric ion (See iron)

Ferrous acetate (See iron ace-

tate)Ferrous sulfate (See iron sul-

fate)Fibers (See also asbestos;

glass) 3>26Fibrils 3Firebrick (See bricks, fire) 5,6Fish oil (See oils, fish)

Florigel (See fuller's earth)

Flue dust, blast furnace 10

Fluorspar (See calcium fluoride)Fluosilicates, alkali 3Fly ash (See ash, fly)

Formal, bis( 2-chloroethyl)- 15Formaldehyde 17,18,19,22,24Formalin (See formaldehyde)Foraamide 9Formic acid 9Foundry cores (See molds)Fuel briquets (See briquets,

fuel)Fuller's earth 6

2-Furaldehyde 26Furan derivatives 16Furfural (See 2-furaldehyde)Furfuryl alcohol 16,26Furnace, electric 6

Galactose 14

Gamma component 20

Generator tar (See tar, gener-

ator)Germanium oxide 4

Glass 3, 6,8Glass, borate 4

Glass fibers 19Glucose 10

Glycerol 16

Glycol esters 16

Glycol, polyalkylene 21

Gold T

Graphite 5,6,7,17,21Graphitic acid 21

Gum arabic 3Gums (See also shellac ; carob

bean gum) 16,21Gypsum 6

Hafnium 7

Hafnium carbide 7Hearth lining 6

Hexachlorocyclohexane (Seecyclohexane, 1,2,3,4, 5, 6-hexa-

chloro-)Hexamethyleneamine (See hexa-

methylenetetramine

)

Hexamethylenetetramine 8,19,23Horizontal retort pitch (See

pitch, horizontal retort)

Hornblende 25

Humates 16

*3

Humic acids 6,l6Hydrates, crystal 7,9,10Hydrocarbons, aromatic, deriva-

tives lk

Hydrocarbons, olefinic 22,26Hydrocarbons, paraffinic 12

Hydroquinone 8 , 19Hydroxy acids (See acids,

hydroxy-

)

Hydroxy amines (See amines,

hydroxy-

)

Inhibitors 4,17Insulators 5,26Iron 7,22Iron acetate, Fe(OAc) 2 6

Iron carbony

1

6

Iron chloride, FeCl3 ^21

Iron humate 6,16Iron ion (III) 16

Iron naphthenate lk

Iron oleate lk

Iron ore 10,17Iron oxide, FeO 6

Iron oxide, Fe3 C>4 8

Iron oxide, Fe2 3 18

Iron sulfate, FeS04 5,8

Isano oil (See oil, Isano)

Kaolin 5

Kerosene 17Ketones 12,1k

Kieselguhr 5,9

Labradorite 25

Lactic acid 10

Latex (See also prickly pear

latex) 21,22,26Lead 7,15Lead naphthenate lk

Lead oleate lk

Lead oxides 9,12,16,17Lead salts 26

Lignin 18,21

Lignite (See also coal, brown)2k

Lignite pitch (See pitch, lig-

nite)Lignite tar (See tar, lignite)

Lignosulfonates 17

Lime 4,5,6,13,1^,26Limestone 6

Lime water (See calcium hy-

droxide )

Linoleic acid, dimer 15Linseed oil 15, 24

Litharge (See lead oxides)Locust bean gum (See carob bean

gum)Low-temperature tar (See tar,

low-temperature

)

Lupines 17

Magnesite 5,6,7,26Magnesium 7Magnesium aluminum silicate (See

attapulgite

)

Magnesium carbonate 8

Magnesium chloride 6

Magnesium oxide 6,7,8,15Magnesium silicate 12

Magnesium sulfate 7Magnets 7,19,22,23Maleic anhydride 16,22Manganese 6,7Manganese chloride, MnCl3 21

Manioc flour (See cassava flour)Mannose Ik

Metal carbides 7Metal carbonyls 7Metal nitrides 7Metal oxides 8,19Metals 6, 7, 8, Ik, 15, 21

Methane, dichloro- 22

Methane , triphenyl , k ,k ' ,k '• -tri

-

isocyanato- 22

Methanol 18

Methylol 26

Mica 26

Mineral aggregates (See aggre-

gates)Mineral fibers (See fibers)

Mineral oil 21

Molasses 10, l6, 17, 21

Molding composition 8

Molding sand (See sand, molding)

Molecular sieves 4,5Molds 15

Molybdenum 7

Molybdenum carbide 7

Molybdenum silicide 9

Mullite k

Naphtha 17

Naphthalene 20

Naphthalene, 1,5-diisocyanato- 22

Naphthalenesulfonyl chloride,

nitro- 21

- kk -

Nickel 7

Niobium 7

Nitrides, metal (See also alum-

inum nitride

)

7Nitrobenzenesulfonyl chloride

(See benzenesulfonyl chloride,

nitro-

)

Nitro compounds Ik

Nitronaphthalenesulfonyl chloride

(See naphthalenesulfonyl chlo-

ride, nitro-)Nitrophenols (See phenols,

nitro-)Novolak 23

Oil, Boleko 15

Oil, Isano 15Oils, drying 15Oils, fish 21

Olefins 22,26Oleic acid 16Oleylamine 12

Olivine 25Ores 5,9;,10,13,17Organosilicons (See silicones,

organosilicons

)

Orthoclase 25

Paint 15Paper 3A5Paraffin wax 23Paving (pavement) 12,25,26Peat 6,24,25Pentaerythritol 22

Petrolatum 2k

Petroleum 6,11,12,13,18,25Petroleum coke (See coke, petro-

leum)Petroleum oxidation products 17,

18Petroleum pitch (See pitch, pe-

troleum)Phenanthrene 20

Phenol 18

Phenol, o-chloro- 19Phenol, U,4'-isopropylidenebis-

2-allyl- 15Phenol-aldehyde resins (See also

novolak) 18,19,22,26Phenol borates 19Phenol- formaldehyde resin (See

phenol-aldehyde resins)Phenol phosphates 19

Phenols (See also phenol-alde-hyde resins) 12,19

Phenols, nitro- 17Phenyl phosphate, mono- 19

Phosphoric acid 4,8,19Phosphoronitrile dichloride 8

Phosphorus pentachloride 8

Pickling wastes (liquors) 8

Pitch (See also next six en-

tries) 11,13,14,19,20,21,22,23,25,26

Pitch coke (See coke, pitch)Pitch, horizontal retort 20,25Pitch, lignite 20

Pitch, petroleum 18,25Pitch, shale 18

Pitch, vertical retort 20

Platinum 7Polyacrylamide (See acrylamide,

poly-

)

Polyalkylene glycol (See glycol,polyalkylene

)

Polyamides (See amides, poly-)Polyester resins (See esters,

poly-

)

Polyethylene oxide (See ethyl-

ene oxide polymers)Polysaccharides 15Polystyrene (See styrene poly-

mers)Polyurethanes (See urethanes,

poly-

)

Polyvinyl acetal (See vinyl ace-tal polymer)

Polyvinyl acetate (See vinylacetate polymer)

Polyvinyl alcohol (See vinyl al-

cohol polymer)Polyvinyl chloride (See vinyl

chloride polymer)Portland cement 8,14Potassium silicate 8,9Potassium sulfate 9Potato starch (See starch, pota-

to)Prickly pear latex 22

Propene 22

Pulp liquor (See sulfite liquor)

Pyrimidines, tetrahydro- 12Pyrobitumens 23Pyromellitic anhydride 15

Quartz 8,15,25

45

Quartz it

e

6

Radiation, protection against 26Refractories 3,4 ,5,6,1,10,16,21Resins (See also epoxy resins;

phenol-aldehyde; urea-formal-dehyde) 7,8,17,19,21,23,26

Resorcinol 8,19Roads 12,25,26Rock 25Rock aggregate (See aggregates)Rubber 19

Salt (See sodium chloride)Salt hydrates (See hydrates,

crystal)Sand 9,15Sand, molding 15, 16Sapphire 21

Sawdust 23Shale 13,23Shale pitch (See pitch, shale)

Shellac 23Silanes (See also alkoxysili-

cons; siliconacylates; sili-

cones; siliconols) 14

Silica (silicon dioxide, Si02 )

(See also quartz) 5,6,7,8,9Silica, colloidal 5,9Silica gel 5

Silicates, alkali (See also

sodium silicate; potassiumsilicate) "

SilicidesSiliconSiliconacylatesSilicon carbideSilicon dioxide

ca)

Silicones (organosilicons)

SiliconolsSilicons, alkoxy

silicons)SilverSoapsSodium aluminateSodium bisulfateSodium carbonateSodium carboxymethylcelluloseSodium chloride 12

Sodium chloroacetate 24

Sodium dichromate 13

Sodium humate 16

3 3,99

7,9IT

>*., 5,7,8,9,19,26(See also sili-

5,7,8,1817,19

17(See alkoxy-

8

It, 25

5

176,24,25

15

Sodium hydroxide21,24

Sodium ionSodium oxideSodium phosphateSodium silicateSodium sulfide, polySoybean oilSoybeansStarchStarch, potatoStearic acidStyreneStyrene polymersSugar

5,13,16,17,18,

16

813

3,6,8,9,1015

15

17,235,l8,23,2U

23,2416

16,22,24,2616,24,26

12,17Sulfides, poly-, of bis(2-chloro-

15

15,16,21,2^,2517

11,22,248,17,18

925

ethyl ) formalSulfite liquorSulfonic acidsSulfurSulfuric acidSuperphosphatesSurface tension

TalcTantalumTantalum carbideTantalum silicideTar 6,11,12,13,16,17

21,25,26Tar acidsTar, generatorTar, horizontal retort

Tar, ligniteTar, low-temperatureTar oils

Tar, woodTartaric acidTartratesTerephthalic acid, dig

esterTetrachloroethane (Se

tetrachloro-)TextilesThickening agent

ThoriumThorium carbide

TinTin aluminateTitaniumTitanium carbide

Titanium oxide

Titanium silicide

97M9

,18,19,20,

18

25

2520

20,2521

18,25,2610

5,26lycidyl

15e ethane,

1521

7

78

3

7

74

9

U6

p-Toluenesulfonyl chloride 21

Trass 5

Tr i ( hydroxyalkyl )dialkylenetri

-

amines 16

k. f k• ,k ' ' -Tri-isocyanatotriphenyl-methane (See methane, tri-

phenyl-

)

Tuff, volcanic (See trass)

Tungsten 7Tungsten carbide ^>6,7Tungsten silicide 9

UraniumUranium carbideUreaUrea-formaldehyde resinsUrethanes, poly-

VanadiumVanadium carbideVermiculiteVertical retort pitch (See

pitch, vertical retort)Vinyl acetal polymerVinyl acetate polymerVinyl alcohol polymerVinyl chlorideVinyl chloride polymerVinyl cyclohexene dioxideVinyl esters

Vinylidene chlorideVinyl polymersViscosity

2616,26

20

Wash oil (See absorption oils)Water glass (See sodium sili-

cate)Wetting agents 8,9White spirit 17Wollastonite 10

Wood 21,23Wood tar (See tar, wood)

7

7

16,24Xylitol 17

19,2622 Zahlit-D 26

Zeolite M7 Zinc aluminate 3

7 Zinc carbonate 8

5 Zinc chloride 7Zinc oxide 8

Zinc stearate 1922 Zinc sulfate 10

22,23 Zirconia (zirconium oxide) k

26 Zirconium 726 Zirconium carbide 7

16,26 Zirconium hydride 715 Zirconium oxide k

26 Zirconium silicide 9