UC SOUTHERN REGIONAL LIBRARY FACIUTY AA 001 185 733 i Issued January 27, 1911. U. S. DEPARTMENT OF AGRICULTURE, OFFICE OF PUBLIC ROADS— Circular No. 93. LOGAN WALLER PAGE, Director. BITUMENS AND THEIR ESSENTIAL CONSTITU- ENTS FOR ROAD CONSTRUCTION AND MAINTENANCE. BY PRfiVOST HUBBARD, CHEMIST, OFFICE OF PUBLIC ROADS. WASHINGTON: GOVERNMENT PRINTING OFFICE. 1911. SRLF 0^ LETTER OF TRANSMITTAL U. S. Department or Agriculture, Office of Public Roads, Washington^ D. C.^ December 5, 1910. Sir: I have the honor to transmit herewith the manuscript of a circular by Mr. Prevost Hubbard, chemist in this office, entitled " Bitumens and Their Essential Constituents for Road Construction and Maintenance." This publication presents in condensed form a description and discussion of various bituminous materials at present in use in road construction and maintenance. It should be of great service in clearing up a very general misunderstanding concerning the actual and comparative value of bituminous road materials, and also the meaning of certain terms. I respectfully request that it be issued as Circular 93 of this office. In view of the newness of the subject and lack of complete data, some of the statements made may in the future require modification. This circular will therefore be revised from time to time in order to keep it abreast with the latest information obtainable. Respectfully, Logan Waller Page, Director. Hon. James Wilson, Secretary of Agriculture. eHOSO"— Cir. 93— 11 3 BITUMENS AND THEIR ESSENTIAL CONSTITUENTS FOR ROAD CONSTRUCTION AND MAINTENANCE. So much confusion exists among road engineers and others in- terested in bituminous road binders concerning the meaning of cer- tain terms as applied to these materials that" it has seemed advisable to present in brief form the definitions of such terms as at present used by the United States Office of Public Roads. It should be un- derstood, however, that these definitions are at present more or less arbitrary, owing to wide differences of opinion held by those who are considered authorities on the subject of bitumens. Notwithstanding these facts, it is hoped that this circular will furnish highway en- gineers and other interested persons with a foundation for acquiring and systematically classifying further information along the lines herein indicated. To aid them in this matter a brief discussion of the value of the various materials used in road construction has been given in addition to the definitions. Acid Sludge. — A mixture of sulphonated hydrocarbons resulting from the treatment of bitumens with sulphuric acid; usually a waste or by-product obtained in this manner from the purification of tar and oil distillates. Wlien sufficiently concentrated these sulphonated products become viscous and gunniiy. They are readily attacked by water and are therefore unsuitable for use as enduring road binders. Anthracene. — A waxy crystalline hydrocarbon having the chemical formula C14H10, found in tars, principally coal tars which have been produced at high temperatures. Anthracene is believed to be of no practical value in road binders. Artificial Asphalt. — See As))lialts and Oil Asphalts. Artificial Bitumens. — Hydrocarbon distillates and residues produced by the partial or fractional distillation of bitumens, and hydrocarbon distillates produced by the destructive distillation of bitumens, i)yro- bitumens, and other organic materials, such as wood, bone, etc. Na- tive bitumens which have been treated merely for the removal of water and extianeous organic and inorganic materials should not l>e classed as artificial products, but as refined native bitumens. Asphalts. — Solid or semisolid native bitumens, consisting of a mix- ture of hydrcK-arbons of complex structnre, largely cyclic and bridge compounds, together with a small proportion of their sulphur and nitrogen derivatives, but free from any appreciable amount of solid [Cir. 0.'!] 5 6 niir.MiNs rou i{t».\i) coNsi itrci ION. parartins, moltini;' upon tlu' applirat imi of lu'iii and cvulcutly pi'o- duoetl by nature from i^etroliMnus coiitainiu": little or no solid paraf- fins. Solitl or stMui>oli(l ivsidut's pi-oduci'd from i)i()l»al)ly similar t>ils by artifu-ial prorossos are sometimes called as|)lialts. hut should more properlv 1h' termed oil as|)halts. 'I'he more rouimou types of native asphalts are known hy the name of tiie locality in which they tH'our, such as Trinidad, lUMinudez. Maracaiho. Cuban. California, etc. Native asphalts with few e.xceptions contain water, extraneous or- ijanic or vephalt. Native asj)halts are usually too hard to be used as road ijinders without tirst fluxing them with a lieavy petroleum residuum and thus j)roducing an asphaltic cement. Artificial asphalts are, as a rule, brought to suitable consistenc}'^ during the process of manufacture. Asphaltenes. — A term commonly aj)plied to those hydrocarbons in petroleums, petroleum products, malthas, asphaltic cements, and solid native bitumens which are soluble in carbon bisulphide but insoluble in paraffin naphtha. As a rule paraffin naphthas of different specific gravities and boiling points dissolve different amounts of hydrocar- bons in a given bitumen, and the heavier the naj)htha and the higher its boiling point the greater is its solvent action. It is evident, there- fore, that the percentage of asphaltenes will vary with the gravity and boiling point of the naphtha, and for this reason it would seem well to substitute for the term asphaltenes, '' bitumen insoluble in paraffin naphtha," with a statement of the gravity of the naphtha used and the temperatures between which it boils. The presence of najihtha insoluble hydrocarbons is supposed to give body to the product in which they occur and to be accountable to a great extent for its binding value. They show no binding value, since many of them are hard and brittle, but they produce adhesive mixtures when fluxed with certain heavy oils. As a rule, for a given type of bitu- men hardness increases with the percentage of bitumen insoluble in a given naphtha. The so-called asphaltenes are not found to any extent in native bitumens with a paraffin base, but occur principally in asphalts, malthas, asphaltic petroleums, and in blown petroleum residues. They vary chemically and physically with the product in which the}' occur, and, therefore, do not represent definite chemical compounds. Asphaltic Petroleums. — Asphaltic petroleums, or asphaltic oils, are petroleums containing an asphaltic base — i. e., they are capable of pro- ducing residues very similar to native asphalts if evaporated or dis- tilled down to the consistency of such asphalts. They contain little ' See Bitumens. [Cir. 93] BITUMENS FOR BOAD CONSTRUCTION. 7 or no solid paraffins and are thus differentiated from paraffin petro- leums. Native asphalts are probably produced from such oils by natural processes. Asphaltic Cement. — The term asphaltic cement was originally applied to a product obtained by fluxing an asphalt with a sufficient quantity of heavy residual oil or flux to produce a binder of suitable con- sistency for paving purposes. In its broadest sense it may be applied to all semisolid bitumens of an asphaltic nature which are of suitable consistency for use as binders in street or road construction, whether prepared by fluxing a solid native or artificial bitumen or by reduc- ing an asphaltic or semiasphaltic petroleum bj^ distillation or other process. Baume Gravity. — An arbitrary scale of specific gravity or density of liquids, usually expressed as degrees Baume or ° B. This scale is commonly used in connection with oil products. For liquids lighter than water the scale begins at 10° B., which represents the specific gravity of water, or 1.0000. As the Baume degrees increase the specific gravity decreases. The following formulae are used in con- verting Baume degrees for liquids lighter than water into direct specific gravity and vice versa : Sp. S'i'' = i3o+oB ^^ 1'^-^'' ^• °B = ^^^^ -130 at 17.5° C. fep. gr. For liquids heavier than water the scale begins at 0° B., which rep- resents the specific gravity of water, or 1.0000. In this scale the degrees Baume increase with the specific gravity. The following formulae are used in converting Baume degrees for liquids heavier than water into direct specific gravity and vice versa : 145 oB = U5-J^^ at 1.5.5° C. bp. gr. Benzol. — A volatile colorless fluid hydrocarbon of characteristic odor having the chemical formula CoHq. It occurs mainly in crude coal tars and water-gas tars, and boils at 80.4° C, so that it is re- moved in the first fraction when these tars are subjected to the process of distillation. Benzol is an active solvent fot most bitumens. It is sometimes called benzene, but should not be confused with benzine, which is the term applied to the lighter and more volatile fractions of petroleum. [Cir. 93] 8 BITUMKNS Von KOAD lONS IIUCTION, Bitumen, -liituiiu'iis arc mixtiirt's of iiativo ov pyro' to materials or objects wliich contain bittmien. such as bituminous rock, bituminous macadam, etc., but also to certain pyro-bitumens, such as bituminous coal, which give rise to the formation of l)itumens upon being sui)jected to the process of destructive distillation. Blown petroleum. — T^lown petroleums, which are often called blowm oils, are ]ieir«)leum rcsiduums through which a jet of air has been passed during or just after distillation. The blowing process causes certain chemical reactions of a complicated nature to take place and results in thickening or increasing the consistency of the oil to an ex- tent depending upon its temperature and the amount of blowing which it receives. Semisolid and solid products are thus often formed from fluid residuums. If the oil is asphaltic or .semiasphaltic in nature, asphaltic cements may be produced in this manner. Blown oils are characteristically short or nonductile when semisolid, although they may possess considerable binding value if not originally of a paraffin nature. Blowing an oil usually increases its percentage of hydrocar- bons insoluble in any given paraffin naphtha. Carbenes. — A term conuuonly applied to those hydrocarbons in pe- troleum, petroleum products, malthas, asphaltic cements, and solid native bitumens which are soluble in carbon bisulphide but insoluble in carbon tetrachloride. The presence of an appreciable amount of these hydrocarbons indicates that the material in which they occur has been subjected to unnecessarily high temperatures. Cracked oil residuums -^how an increase in carbenes in proportion to the extent of cracking and the formation of these products is evidently a near step to coking. But little is known of their effect upon the value of a bitumen for road construction, but they are generallv looked upon with suspicion and, in certain specifications for asphaltic cements, their prc See Refined tar. [Cir. 9:1] 10 UnrMKNS Ft»IJ ItoAD (ONsnU'c IMON. niul >ho\\>. a lii«:lu'r raiio of r:irl)t)ii to livdro^t-ii than tlu* ori<2;iniil uioKh-uK', ov t'lsi> ill tlu> ili>ni|)lioii of tli.> luolfciilc iulo its cliMuonts, livdroiTon aiul c-arboii. In tho latlor case tho proi-rss is said to bo lU'stnu'tivo. I'll*' nioiT Nolatilc ami cluMnicaliy stable hyib'ocarbons can Ih» orurkoti onlv at tt'inpnat uro aboxc tlicii- lioilini,^ points. In tlu> ilistillation of oils this is arfoniplishi'd bv c-ausin^^ condonsation to take plaiv in the still luul nllo\vin«; tlu* condensed oils to fall back into the residue, the temperature of which is considerably higher than their boilin*; points. In i-arbureted water-nfas manufacture, oils are cracked by vaporizin<; them at a nnich hi iu)t null roailily, but iiitunicsccs at hiirh temperatures. It is tlitferentinted from ixilsonitc and the ii:i(i\i' asphalts by the fact that it is almost insoluble in paratlin naphtha. It has been produced at hi«rh temperatures, as e\ idenced by the percentage of cnrbenes which it contains, and some varieties closely approach the pyro- bitumens in characteristics. It has been used to s coNsrurcrioN. poratmvs. Oil (Hi's are usually l>v-|>n)«ln<'ts of (lip lUiunifacluro of oil pis or carluirottvl waltM* pis. Paraffin Naphthas.- Naphthas consist iniil»'il ovov tho I'liited Siatt'.< iuul varv from nuk whifh is frinltlf ami wholly drpiMulont uj)oii tilt' bitumen to hold the iniiiiMid l"i:iu:iu»'ii(s tojiri'tluM' to solid riH'k lmviii«: nioivly its intt>rs(iiTs lilK'd with hitiiiiuMi, Tlu' fonuer ty^K" is i>f valiio for uso as a surfan* hiiulor in (he eonst ruction of roads when the maltha shows jjood bindin*; value and amounts to not le-^ thun (■' |H r <«Mit of tlu' wciijht of ro*'k asphalt. Semiasphaltic Petroleums. Scmiasphallic petroleums or semi- asphiiltie oil>- are petroK'ums containiuir a seuiiasphaltie base, i. e., petroleums whose residues j)rodueed l)y e\aporation or distillation, while itunpost'd mainly of asphalt ic hydrcKarbons, contain also a cer- tain pen^entrt^e of paralVm wax. They thus show a mixed base. If tlu'ir percentale only as a dust palliative in the surface treatment of roads. When reduced to proper consistency by distillation, how- ever, it shows certain desirable properties for use as a road binder both for surface treatment and macadam construction. AVater-gas tar may also be used in the preparation of road binders from high- carbon coal tars. "When this is done, the two crude tars are mixed in such proportion that when distilled to the desired consistency the mix- ture will contain le.ss than the maximum limit of free carbon allowable. [Cir. ft.l] o