November 15,1934
IN D U ST R I A L A N D E N G IN EE R I N G CH E M IS TR Y
excess silver is removed with sodium chloride and the fluorine in the filtrate is determined as follows (6): Ammonium hydroxide is added in excess and the solution boiled down to 40-50 CC. A 7.0-em. ashless filter paper is added and thoroughly macerated and 10 cc. of 2 N calcium nitrate are added t o the hot solution t o precipitate the fluorine. The solution is cooled, filtered, and washed (filtrate and washing should not exceed 100 cc.). The residue is ashed in a platinum crucible and weighed as calcium fluoride. Data on the accuracy of such fluorine determinations are given in Table V. TABLEV. DETERMINATION OF FLUORINE --SAMPLE-
Sodium fluoride Gram 0.0125 0.0153 0.0216
Wood Grams 3.8 5.0 5.0
413
LITERATURE CITED (1) Am. Wood Preservers’ Assoc., “Manual of Recommended Practice,” Washington, D. C. (2) Bateman, E., INn. ENG.C H ~ M6, . , 17 (1914). (3) Cone, W. H., and Cndy, L. C., J. Am. Chem. Sac., 4 9 , 3 5 6 (1927). (4) Hawley, F. A., INn. ENG.CHEW,18, 573 (1926). (5) Leach, A. E., “Food Inspection and Analysis,” 4th ed., p. 886, John Wiley & Sons, N. Y . , 1920. (6) Pflaum, D. J., and Wenzke, H. H., IND. ENG.CHQM.,Anal. Ed., 4, 392 (1932).
(7) Richards, C. A., Proc. Amer. Wood Preservers’ Assoc., 127 (1923).
Gram 0.0110
(8) Treadwell, S. P., and Hall, W. T., “Analytical Chemistry,” 7th ed., Vol. 11, p. 203, John Wiley & Sons, pu’. Y . , 1929. (9) Waterman, R. E., and Wells, C. O., IND. EXG.CHEM.,Anal. Ed., 6, 310 (1934).
0.0114 0.0183
RIPCEIVED April 14. 1934.
Sonrnai FLUORIDE FOUND
IV. Small Sapling Method of Evaluating Wood Preservatives ROBERT E. WATERMAN AND R. R. WILLIAMS, Bell Telephone Laboratories, New York, N. Y.
P
ERMANEXCE and
I n order to expedite tests of the permanency effective ratio perhaps to 9 or 10. However, other factors, notably toxicity are probably the of Pole preservatives, use is made of groups of longitudinal diffusion from below most necessary characsmall pine saplings treated with the preservative ground upward, further compliteristics of a wood preservacate the comparison and prohibit in question and set in the ground as miniature an exact treatment of it.) The tive. E a s e of injection, freesaplings are easy t o obtain, and telephone poles, In these specimens weathering dom from corrosive properties, are better than turned sticks in cleanliness, cost, and the like is relatively rapid on account of the large ratio of that they approximate a pole in are all important, b u t no surface to volume, and poorly preserved material which the grain runs parallel t o the surface. The saplings rarely, material can be considered unbegins to decay in ‘i or 2 years. Analyses and if contain any heartwood less it displays a high degree of toxicity tests as well as observations of decay and a r e easily impregnated resistance to wood-destroying throughout. are made periodically. Seven years’ experience fungi and u n l e s s t h i s toxic The usual procedure has been potency persists when t h e indicates that the comparative preservative values to inject three dozen air-dried treated wood is exposed to the of various salts, creosotes, oils, etc., may be ~~~~~~~~~~~~~~~~~~~~i~~ w e a t h e r f o r l o n g periods of estimated relatively cheaply, quickly, and with ture treating plant using the full time. The problem under discell process. After discarding the considerable reliability by this method. cussion is that of appraisal of butt 3 inches (7.62 em.), the next 3 inches (7.62 cm.) are cut off for wood preservatives f o r t h e s e analysis, or for extraction and toximetry. (The preservative contwo characteristics within a reasonably short time. tent tends to be higher in the upper part than in the butt. The Methods are gradually becoming standardized for toxi- same is significantly true for full-sized poles However, in both metric determinations and if this were the sole considera- case8 we are interested chieflv in rates of dedetion at the ground tion, judging preservatives would be greatly simplified. line which is nearer the butt.“) A dozen of fhe saplings c h t o a However, permanence is equally important and is more length of 30 inches (76.2 cm.) are set in the ground, butt down, each of three test plots which are maintained at Limon, Colo.; difficult to estimate. It may be measured to a degree by in Chester, N. J.; and Gulfport, Miss. Such quick and consistent laboratory determination of the evaporation and leaching results are obtained at the last-named location that the other rates of oils and salts, respectively, but a true measure of the test plots are now less used for this particular work. Comparautility of a preservative should include something closely tive data at the three plots have, however, furnished a rough calibration of climatic influence on the test. Untreated saplings resembling outdoor exposure and a measurement of the rate at Gulfport have always failed completely within a year either of decline in amount and potency of the preservative. Prefer- by rot or termite attack or both. All tests reported herein were ably these observations should be extended till actual rotting made at the. southern test plot. occurs, a t least in the case of less satisfactory products. The sapling form of specimen and its method of exposure In dealing with such a complicated chemical, physical, and biological process, laboratory tests have definite handicaps is clearly imitative of a telephone pole. The contact with and it is always possible that some vital factor has been the soil and consequent leaching effect below ground and missed. A complete life observation within a short time is the exposure of the upper part of the sapling to the evaporathe end to be desired and the use of small specimens exposed tive effects of the air are both essential features of the exposure. The data so obtained provide a well-rounded picture to a warm moist climate permits an approach to this ideal. of the virtues and shortcomings for pole preservation purposes The method chosen makes use of small saplings of southern of each preservative. Naturally, the effects of ground water yellow pine about 0.5 inch (1.27 cm.) to 0.75 inch (1.94 om.) in extend up into a sapling farther in proportion to its total diameter and 30 inches (76.2 cm.) long. The ratio of surface length than is the case with a pole, so that one must be caret o volume, expressed in inches, in the average pole in use in the Bell System is approximately 0.467. In a sapling of 0.75 inch ful not to carry the parallelism too far in interpreting ground(1.94 cm.) diameter this ratio is 5.33. Hence for a given unit line effects. of volume the sapling has a surface available for evaporation The specimens are examined for rot and insect attack a t or leaching 11.42 times as large as the average pole with a diam- least once a year. On each inspection one or more from each eter of 8.56 inches (21.7 cm.) and accordingly tends to rot much sooner. (The treated volume of wood in a pole is normally group may be removed for laboratory examination. Chemisomewhat smaller than the total volume, thus reducing the cal or biological assay of these saplings affords evidence
Vol. 6, No. 6
ANALYTICAL EDITION
414
In Figures 3 to 8 each vertical line of squares represents the status of the group of saplings on the occasion of a particular inspection. Thus in series CU, Fi re 3, at the end of 2 years, 2 sa lings were broken or lost, 1ha&een removed in a suspicious eonfition, and 1had been removed in a sound state for analysis. Of t,he remaining saplings 5 were sound and 1 suspicious. The saplings are arranged in each vertical column in descending order of soundness, so that the cumulative extent of decay is seen at a glance as a massed cross hatching at the bottom of each series. The horizontal rows of squares therefore do not indicate the progress of decay in a particular specimen. All concentrations of preservatives are stated in grams of preservative per 100 cc. of total wood volume. One gram per 100 cc. equals 0.625 pound per cubic foot. Series marked “e” were impregnated by an empty-cell process, others by the full-cell process.
DISCUSSION OF RESULTS Water-soluble salts have proved comparatively impermanent in the sapling tests (Figure 3), owing largely to the leaching out of the salts both above and below ground (Table I). The results with saplings are in harmony with commercial experience with poles correspondingly treated,
FIGURE 1. TREATED SAPLINGS Left freshly treated saplings, ready for analysis and subsequent exposure. Rikht, weathered saplings, showing decay and termite attack in butts.
of the rate of depletion and some indication of progress towards the decay stage. Within the first year, it is usually possible to tell by analytical means whether or not the material has promise. In extreme cases failure takes place during this period. Usually the leas successful preservatives are attacked by insects or rot during their second year. In order to save space the results of the field inspections have been shown in a graphic manner in Figures 3 to 8. The analytical results given in Tables I to V include with a few exceptions only those saplings which have been removed while still sound. The exceptions represent failures which had some special feature of interest. The analytical methods used have been described in a previous paper.’ 1 Waterman, Koch, and McMahon, IND.ENB.CHEIM., Anal. Ed., 6, 409 (1934).
FIGURE 2. SAPLINGTESTPLOT, GULFPORT, MISS. in so far as the materials involved have had a commercial use in similar exposures. Mercury and copper treatments are more permanent in preventing decay of saplings than other soluble salts, thus conforming to the implications of the extensive and relatively satisfactory European experience with these salts in pole treatments. Probably some portion of the heavy metals is more or less definitely adsorbed on the fibers. Saplings treated with mercury and copper salts are
TABLEI. ANALYTICALRESULTSON SELECT~D SPECIMBNSUSING“WATER-SOLUBLE” SALTTREATMENTS FINALCONCENTRATION FINALCONCINTRATION Y I A R ~ ORIQINAL Above Below CONDITION YEARE ORIGINAL Above Below CONDITION SPECIMENUNDER CONCBN- ground ground OF ANALYZED SPECIMEN UNDIR CONCSNground ground OF ANALYZIOD NUMBER TssT TRATION line line SPECIMEN NUMBBR TBBT TRATION line line SPBCIMBN a./ioo c ~ . * a./ioo cc.* Q . / l O O cc.* U . / l O O cc.* SER110 1-16,
6
As zinc 2.64 1.28 2.48 2.28 2.50
11 13 15
2.51 2.72 2.05
49 50 52 60
As zinc 0.65 1.23 1.02 0.96
1 2 3 5
a
As zinc 0.222
.... 0.081
Nil 0.058 0.053 0.120 0.080 0.093
2.46
SlPRIBS
1
1
2 2
C,
SERIE8 AO. SODIUM AREINITB
ZINC CHLORIDl
d.’i&
0.082 0.014 0.053 0,029 0.048 0.053 0.043
Sound Bound Sound Rotted Sound Rotted Termites Rotted Rotted
2
1 1
4.57 4.43
6
18
*
..
-
1 1
AB AszOt 0.27 0.34
0lRIgE
As zinc 0.088 0.067 0.089 0.076 0.078 0.066 0.045
....
Sound Sound Sound Slight decay
0.027 0.086
0.027 0.013
Rotted Rotted
2
Njl Nil Trace per C U ~ft.
Nil Nil
....
AS AmOa -.. 0.0056 0.0021 0.0035 0.0008 0.0013 0.0011
NA,
AS AanOs 0.0042 0.0011 0.0048 0.0008
Rotted Rotted Rotted
8181108
3 5
7
10
Sound Rotted
PARTIALLY NBUTRALIZID SODIUM ARSENITE
Aa AsnO; 2.32 2.40
As AstOs 0.086 0.0043 0.030 0.0180 CU,
As copper
SBRIBIE IN, SODIUM TLUORIDB
3 1 0.86 17 1 1.92 32 1 1 gram per 100 cc. 0.825 lb.
1 1 1
SlPRIIS AR, AR0INOU0 ACID
#INC CHLORIDlP
S I R I I S BO, BORAX
15
3 7 10
As AaiOa 0.90 1.36 1.28
0.77 0.64 0.50 0.45
Slight decay Sound
COPPBR BULPATB
A0 Copper 0.118 0.045 0.048 0.058 0.102 0.082 0.077 0.088
Sound Sound Sound Suspicious
SBRIES HQ, MBRCURIC CHLORIDl
Termites Termites Termites
As mercury 1
16
0.32 0.24 0.40
As mercury 0.056 0.022 0.083 0.061 0.104 0.106
Sound Sound Suspicious
415
I N DUSTR I A L A N D E N GIN EEK 1N G CHEMISTRY
November 15,1934
the case of some preservatives the depletion as shown by analysis is marked; in others rot is observed in spite of the continued presence of substantial amounts of preservative.
SLRIES 1-16 ZINC CHLORIDE 2 27 GRAMS SERIES I N SODIUM FLUORIDE SERICS BO BORAX 4 05 GRAUS
SERIES Ce ZINC CHLORIDE 0 9 6 GRAMS
SERIES A0 SODIUM ARSENITE 0 08 GRAMS
SERIES AR ARSENOUS ACID 0.30 GRAMS
TABLE11. ANALYTICALRESULTSON SELECTED SPECIMENS USING“WATER-INSOLUBLE” SALTTREATMENTS FINALCONCENTRATION Below CONDITION Above ground OF ANALYZED ground line SPECIMEN line
YEARS ORIGINAL CONCENSPECIMEN UNDER NUMBERTERT TRATION G./100 ec.*
G./i00 ec.*
RERIES B, BARIUM HYDROXIDE
6 18 1
2
3
I
5
4
2
3
4
2
8ERIH18 U, ZINC METAARSENITE
As Zn As Zn basis basis basis basis 1.15 0.30 0.172 0.14 1.18 0.64 0.166 0.46 1.41 0.90 0.178 0.64
Zn SERIES NA PARTIALLY NEUTRALIZED SODIUM ARSENITE 2.43 GRAMS A S 2 0 3
SERIES nG MERCURIC CHLORIDE 0 38 GRAMS HC
SERIES CU COFFER SULFHATL 0.54 GRAMS Cu
1 1
1
2
3
1
4
2 3 4 5 TIME IN YEARS
3 4
EACH SQUARE REPRESENTS ONE SMALL SAPLING
0SOUND
2
3
5 6 8 9 24
$:I%%ACK SEVERE ATTACK
1
2
LOST OR BROKEN
3
4
4
5
6
KEY EACH SOUARE REPRESENTS ONE SMALL SAPLING
SERIES 1E ZINC CYANIDE
2
5
1
, 2 3 4 TIME I N YEARS
0
SOUND
p J
susPIc1ous
?%L
BTAcK
SEVERE ATTACl( LOST OR BROKEN 3
4
Sound
Sound
Cu Zn Cu Zn Cu Zn 0.115 0.107 0.083 0.094 0.072 0.056 0.101 0.107 0.083 0.085 0.082 0.080 0.102 0.096 0.086 0.056 0.082 0.026 0.097 0.101 0.078 0.058 0.075 0.038 0.101 0.112 0.102 0.063 0.112 0.016
1 1 2 2 3
Sound Sound Sound Sound Sound
SERIES lB, ZINC CHLORIDE-SODIUM CYANIDE
5
3 4 5 6 TIME IN YEARS
SERIES I B ZINC CHLORIDESODIUM CYANIDE
I
2
Sound
0 SAMPLE REMOVED
2
1 1
As basis 0.078 0.109 0.075
SERI1S Z, AMMONIACAL SOLUTION OB COPPER AND ZINC ET!DROXIDER
susPlcloUs
SERIES Z COPPER 0102 GRAMS ZINC 0 I06 GRAMS
1
1
basis 1.12 1.13 1.39
1 1 2
6
2 10
FIGURE 3. FIELDEXPOSURES OF SAPLINGS TREATED a‘ITH WATER-SOLUBLE SALTS SERIES 0 OA RlUM HYDROXIDE 1 2 0 GRAUS SERIES U ZINC META ARSENITE
Rotted Rotted
0.42 0.30
0.54 0.77
1.31 1.17
1 1
3 4 TIME I N YE4\R S
1
0 SAMPLE REMOVED
Zn 0.138 0.222
Zn 0.085 0.186
Sound Rotted
SERXE8 1 1 , ZINC CYANIDE
Zn Zn 0.339 0.484 5 1.5 0.365 0.442 12 2 0.370 0.544 16 1 * 1 gram per 100 cc. = 0.626lb. per cu. ft.
noticeably brittle above ground line. Cotton treated with c o p p e r s u l fate and dried has also been found to be markedly t e n dered. These f a c t s are suggestive of a chemical action on cellulose in both wood and textile fiber. In confirmation of the sapling results with t h e soluble arsenic compounds,it may be said that 6-inch
Zn 0.191 0.230 0.193
Sound Sound Sound
The sapling results with two of the water-insoluble salts have also been checked by similar exposures at the same site of posts of %inch (20.6-cm.) diameter similarly treated in order to appraise further the merits of the sapling method of testing. Such posts, containing 0.48 gram of zinc metaarsenite per 100 cc. of total wood volume, lost about 80 per cent of the arsenic and about 40 per cent of the zinc below ground in 18 months. The losses above ground were much less. After 30 months, superficial decay was present below ground in 8 out of 14 posts; at 38 months, 13 showed some decay, 11 exhibiting disintegration up to a depth of 1 inch (2.54 cm.) ; a t 60 months all showed decay; the only post removed for complete examination at this time showed rot throughout the sapwood a t the butt. These results with posts are in reasonable agreement with those obtained with
FIGURE4. FIELDEXPOSURES OF SAPTREATED WITH WATER-INSOLUBLE SERIES 4 4 - 5 5 SALTS LIQUID GRADE
LINGS
SERiES E e MODERATELY HIGH RESIDUE CREOSOTE I O 7 GRAMS
CREOSOTE
(15.23-cm.) diameter posts treated with solutions containing arsenous oxide and others treated with a partially neutralized solution of arsenous oxide (Figure 3) showed definite signs of decay after 4 years in the ground a t the same site. The other water-soluble salts used in saplings were not tested by exposure of post specimens, as this class of salts was not considered sufficiently promising for long-life treatments to justify the expense of such tests. Under “water-insoluble” salts various compounds are included which are used in water solution but afterwards tend to become sparingly soluble by evaporation of a constituent or by reaction with the air or the wood. The extent of losses by leaching is indicated in Table I1and the evidence of permanence of resistance to decay in Figure 4. In
Zn 0.294 0.271
2 1
SERIES 0 LOW RESIDUE CREOSOTE
SERIES pe LOW RESIDUE CREOSOTE 9 P GRAMS
SERIES R MODERATELY HIGH RESIDUE CREOSOTE 19.5 GRAMS
SERIES 0 MIXTURE OF HIGH AND LOW RESIDUE CREOSOTE
0 O 0
1
2
3 1 1 Ill I I Ill
0 0 0 0 0 0 0 0 0 0 O O 0 0 0
0
0
3
4
0
0
0
5
6
7
1
I
2
3
4
5
2
3
4
5
6
1
2
3
4
5
1 2 3 1 5 6
6
1
6
2
3
4
5
6
TIME IN YEARS
SERIES I J e HOR RETORT COAL TAR CREOSOTE 7.7 GRAMS
SERIES I K e OVEN COAL TAR CREOSOTE 6 . 0 GRAMS
SERIES )Me VERT. RETORT COAL TAR CREOSOTE 10 2 GRAMS
SERIES > w e GAS WORKS COAL TAR CREOSOTE 10.4 GRAMS
SERIES K LOW RESIDUE CREOSOTE 4 4 . 5 GPAMS
1
2
3
4
5
6
I
2
3
4
1
2
3
4
1
2
3
EACHKEY SOUARE REPRESENTS ONE SMALL SAPLING
0SOUND
Ea
susPIcIous
I Rkb4dL ;?TACK SEVERE ATTACK 0 SAMPLE REMOVED
4
TIME I N Y F A R S
OF SAPLINGS TREATED WITH COAL-TAR CREOSOTES FIGURE 5. FIELDEXPOSURES
Vol. 6, No. 6
ANALYTICAL EDITION
416 SERIES 1 1 1 D
0.18 GRAMS
mmm
SERIES I f 5 D 0.0 GRAMS
SERIESlT2 0 0.32 GRPMS
Y R I E S IS
SERIES IT 2.6'GRAMS
SERIES IT10 D 1.6 GRAMS
3.7* GRAMS
rll-rnnm
nnmnm
TABLE111. ANALYTICAL RESULTS ON SELECTED SPECIMENS USINGCOAL-TAR CREOSOTE TREATMENTS YBARB SPECIMENUNDER NUMBER TEST
FINALCONCBNTRATION
ORIQINAL
CONCENTRATION
Above ground line
a./roo
G./iOO cc.* 1 1 5 2
, 1 5 2 3
1 1 5 2
1 1 5 2 3 d
I 1 5 2 3 4 TIME IN YEARS
STRAIGHT TREATMENTS- SERIES P AND D
44 45 46 47 48 49 55
KEV EACH SQUARE REPRESENTS ONE SMIILL SAPLING
SERICS 0
SERIES P e
BERIB8 44-55,
1 1 5 2 3 4
1 1 1 2 2 3 4
Below ground line
CONDITION
ANALYZED SPECIMEN
OF
cc.*
LIQUID CREOBOTE
60.6 59.8 44.2 50.9 57.0 52.4 49.8
42.8 31.2 27.3 31.2 42.8 27.2 35.8
Sound Sound Sound Sound Sound Sound Sound
54.6 50.0 49.5 33.3 41.7 45.4 24.5
SERIEB D, MIXTURE OF HIQH- AND LOW-REBIDUB CREOBOTES
17 18 20 21 28
MEDIUM ATTACK SEVERE ATTACK SAMPLE REMOVED
1 1 2 2 3
30.7 51.6 41.2 31.5 55.4
29.3 45.3 21.6 24.2 18.4
BERIEB E , MODERATELY HIQH-REBIDUE 1
FIGURE 6.
2
3
4
5 6 1 2 3 T I M E I N YEARS
4
5
1 3 4 9 11 21
8
FIELDEXPOSURES OF SAPLINGS SHOWINQ EFFECT OF CONCENTRATION OF CREOSOTE
1 1 2 2 3 3
8.5 5.6 10.1 8.6 10.1 12.6
5.3 1.9 5.4 4.2 5.6 3.4
1 3 4 5 24
1 2 2 3
1
6 7 8 10
1 1 2 2
1 6
1
24.2 17.3 14.5 16.3 15.5
17.1 7.0 10.1 9.1 7.7
CREOBOTE
Sound Sound Sound Sound Rotted Suspicious
4.3 3.5 4.8 4.5 6.1 2.6
BERIEB R, MODERATELY BIQB-RESIDUE
saplings (Figure 4). The relative life of the saplings has presumably been prolonged by the fact that they contained about 1.36 grams per 100 cc. of the preservative while the posts contained less. On the other hand, posts treated with an ammoniacal solution of copper and zinc hydroxides (Figure 4, Series Z) d e cayed approximately as fast as saplings similarly treated, Among 25 posts exposed, 1 showed decay at the end of 2 years, 14 a t 4 years, and 15 a t about 7 years, the decay being largely below ground. In the case of saplings, evidence is given that loss of resistance is not due to extensive leaching of the metallic components (Table 11, Series 2). The posts were also analyzed and showed little loss of copper or zinc over a period of 4 years. Decay is apparently due in both cases to gradual conversion of the hydroxides to the insoluble oxides which are very slightly toxic on account of their low solubilities. Such a reaction is very little influenced by the size of the piece and the behavior of the saplings must be regarded as consistent with that of the posts in this instance also. These incidents, however, make clear the
Sound Sound Sound Sound Sound
18.1 50.0 28.0 24.6 26.8
CREOSOTI
15.8 10.6 9.4 12.1 5.3
Sound Sound Sound Sound Sound
BERIEB P, LOW-REBIDUE CREOBOTE
13 22
1 2 2 3
33 34 38 43
1 1 2 3
9
9.1 10.8 14.7 14.2
7.2 5.8 2.9 4.8
3.7 5.6 2.4 3.8
BIRIEB 0, LOW-REBIDUI
CREOBOTB
22.5 26.2 28.2 26.3 15.6 15.8 45.4 27.1 25.0 48.1 10.7 19.9 45.0 19.1 21.1 a m m s K, LOW-RESIDUE CREOBOTE 54.1 41.1 39.4 48.2 37.1 36.8 48.8 20.5 18.9 50.6 16.8 24.5
Sound Sound Sound Sound Sound Sound Sound Sound Sound Sound Sound Sound Sound
lERIE8 IS, HORIZONTAL RETORT COAL-TAR CREOSOTE
1 34 36
2 1 1
9 32 35
2 1 1
7.4 7.7' 7.7"
2.6 5.5 4.3
1.8 4.8 4.3
Sound Sound Sound
BBRIES l K , OVEN COAL-TAR CREOBOTE
5.6 8.0" 8.0"
2.4 5.3 5.6
2.1 6.9 6.1
Slight decay Sound Sound
BERIBS IM, VBRTICAL RETORT COAL-TAB CREOBOTB SERIES 17-32 LOW TEMPERATURE TAR CREOSOTE 48.5 GRAMS
3 33 35 SERIES L LOW TEMPERATURE TAR CREOSOTE
SERIES 3 3 - 4 3 BLEND OF HIGH AND LOW TEMPERATURE TAR CREOSOTES SERIES G WATER GAS TAR CREOSOTE IO 2 GRAMS
2 1
1
9.0 10.15 10.1"
3.4 8.2 7.4
3.0 6.4 5.8
Sound Sound Sound
BBRIB8 l W , QABWORXB COAL-TAR CREOBOTBl
7 2 9.3 30 1 10.4" 34 1 10.4" 1 gram per 100 ca. = 0.625 lb. per 0 Average of charge.
*
4.2 9.0 6.1 cu. ft.
3.4 7.8 5.0
Sound Sound Sound
necessity of supplementing the exposure of saplings by periodic analyses to secure a true interpretation of results.
OILS 1
1
3
4
5 8 7 I 2 TIME IN Y fU R S
SERIES ine SERIES I G ~ WATER GAS WATER GAS TAR CREOSOTE TAR CREOSOTE SAMPLE 2 SAMPLE 1 6.0 GRAMS 8.0 GRAMS
0
0
0
0
0
2
2
3
4
5
6
1
Te Low SERIES 7EMPE~A,VR~
2
3
4
5
6
SERIES I L ~ WATER GAS TAR CREOSOTE SAMPLE 3 6,7GRAMS
1
2
3
4
5
6
KEY EACH So"ARE REPRESENTS ONE SMALL SAPLING
O SAMPLE REMOVED
2
3
4
1
2
3
4
1
2
3
4
TiME iN YEAFIS
FIGURE 7. FIELDEXPOSURES OF SAPLINGS TREATED WXTE VARIOUSCREOSOTES
Experimental work on oily preservatives has been greatly complicated by difficulties of control of the amount of preservative introduced into the saplings. Some of the earlier series, such as 17 to 32, Figure 7, and 44 to 55, Figure 5 , were full-cell treated and contain so much creosote that they will, when the experiment is finished, merely serve to indicate how long saplings can be preserved with large amounts of creosote. Such results will have some value as a norm of extremely good preservation and to illustrate the loss of creosote from wood exposed to the weather. Later emptycell methods were used with somewhat better success. However, some experiments, such as 0 and R, Figure 5, still failed because of lack of control of retent to bring out satisfactorily the comparison which was intended-in this case that of one kind of creosote with another kind. There has
November
I N DUSTR I A L AN D EN GIN EER I N G CH EMISTR Y
15,1934
417
RESULTSON SELECTED SPECIMENS TABLEIv. ANALYTICALRESULTSON SELECTED SPECIMEN6 TABLEV. ANALYTICAL WITH SPECIAL OILS, MIXTURES,ETC. USINQWATER-GAB AND LOW-TEMPERATURE TARCREOSOTE USINGTREATMENTS TREATMENTS FINALCONCENTRATION YEARS ORIQINAL FINALCONCENTRATION CONCENAbove Below CONDITION SPECIMEN UNDER T ~ S T TRATION NUMBER CONCBN- ground ground OF ANALYZED TRATION line line SPECIMEN 0./100 cc.*
YEARS
ORIQINAL
SPHICIMBN UNDER NUMBER TEST
G./lOO cc.*
G./lOO cc.* SERIES
17 18 19 20 21 22 23 32
n-az,
1
LOW-TEMPERATURE
48.5" 46.9 41.9 45.1 54.1 55.5 52.2 51.7
1 1 2 1 3 3 4
15.8 23.8 16.8 20.3 24.8 15.8 19.4 17.4
1 1 1 2 3 4
3 5 7
1 1 3
47.7 34.9 35.7 53.0 31.8 41.4
31.4 14.9 22.6 22.6 24.0 21.9
Sound Sound Sound Sound Sound Sound Sound Sound
21.8 34.9 25.1 30.2 29.3 16.5 22.4 5.8
1.3 1.1 0.9
1 1 2 2 3
49.9 53.6 60.0 46.6 34.5
57.0 58.2 34.2 30.2 34.7
Sound Sound Sound Sound Sound
53.3 54.6 47.3 43.7 31.2
4 5 6
8 19
12.5 11.2 16.3 8.8 19.2
10.7 13.1 14.1 6.1
6.1
1 2 10
1
1 2 1
2 4 5
1 2
3 5 9
1 2 1
2 1 1
1
2
26 27
1
4
1
5.3 5.9a 5.9a
2.9 5.1 3.2
1 1 2
1
3.1 3.7 2.2
1 2
Sound Sound Sound
10
1 1 2
8
a
1 36 86 1 * 1 gram per 100 eo. 0 Average of charge.
-
2.7 3.2 4.2 9.0 cu. ft.
Sound
Sound
Sound Sound Sound
WAX-CREOSOTE MIXTURE
6.4 5.1
5.0 5.9
Sound Sound
25.8 17.8 27.0
14.4 10.4 10.7
17.9 12.3 12.5
Sound Sound Sound
7.7 9.3 9.8
5.8 5.3 5.1
3.7 4.2 2.7
Sound Sound Sound
35.7 50.6 40.3
28.0 26.9 26.2
29.6 18.6 30.1
Sound
Sound
Sound
24.0 17.6 25.6
23.8 18.1 25.1
35.4 21.6 43.5
Sound Suspicious Suspicious
Slight decay Sound Sound
4 7 10
1 1 2
Slight decay Sound Sound Sound
1
1 1 2
27.5 26.7 26.7
29.1 21.9 23.4
25.3 25.9 17.9
Sound Sound Sound
BERIES CE, WATER-QAB TAR
0.8 1.8 2.1
11.2 9.3 9.9
5.0 2.7 2.7
Sound Sound Sound
18.5 19.9 19.0
Sound Sound Sound
11.0 3.2 3.0
SERIES PQ, WATER-QAS TAR
BERIBB l L , WATER-QAB TAR DISTILLATE
6.1 5.8 6.7" 6.7" 0.625 lb. per
44.8 21.6 42.0 44.3 28.0
%ERIES CQ, WATER-QAS TAR
0.6 3.8 2.6
8mRims IH. WATER-BAS TAR DISTILLATE
5:6 5.9a 5.95
OIL MIXTURE
SERIES CA, CRUDE OIL-NAPHTHALENE-ANTHRACBNB
1 3 10
BERIES 1Q. WATER-QAS TAR DISTILLATE
10 29 30
i:7
Sound Sound Sound Sound Sound
SERIES CN, CRUDHI OIL-NAPHTHALENE
Sound Sound Sound Sound Sound
11.4 11.4 8.6 3.5 3.8
1 1
21.0 23.2 13.3 15.4 10.1
8ERIBB WE, WOOD-TAR CREOSOTE
SBRIBS T, LOW-TEMPERATURHI TAR CREOBOTHI
1 1 2 2 3
ANALYZED SPBCIMEN
EERIE8 WT. WOOD-TAR CREOSOTE
BERIEB L, LOW-TEMPERATURE TAR CREOSOTE
1 2 3 5 22
14 15
BEBlEB M, EG-40
Sound Sound Rotted
1.8 1.9 1.0
23.4 19.7 26.6 58.6 33.5 19.4 49.2 12.6 23.4 11.7 smsms x, CREOSOTE-CRUDE 50.0 45.8 51.0 21.9 48.7 45.2 51.7 42.7 34.3 31.4
a
4 12
3
Sound Sound Sound Sound Sound Sound
28.6 19.7 31.7 33.6 18.4 30.2
1 1 2 2 1 1 2 2 3
1
2
SERIES 0, WATER-GAB TAR DISTILLATE
5.7 8.6 5.1
CONDITION
OF
SERIES F. TAR ACID FREED CREOSOTB
1 2 3 4 22
TAR CREOSOTE
SERIBB a3-48, BLBND OF HIGH- AND LOW-TEMPERATURE TAR CREOBOTES
33 34 35 37 38 43
Below Above ground ground line line G./lOO cc.*
0.4 1.9 1.8 3.8
2 10
34.6 28.0 44.2
31.8 26.9 16.3
EERIE8 Pa, WATER-GAB TAR
5.1 2 7.7 6 7.2 1 8.0 8 11.7 1 10.2 10 1 gram per 100 cc. = 0.625 lb. per ou. ft.
4.3 6.4 5.1
Sound Sound Sound
* been a constant effort to standardize an empty-cell process of impregnating saplings with oil, but experience shows that the same treatment with two oils of different composition accumulations of evidence from year to year. The toluene often results in dissimilar retents. The authors believe that evaporates quickly and does not seem to influence the this is tximarily due to differences in viscosity of the oils results of exposure. The toluene dilution method is now manifeshg themselves in the kick-back SERIES X SERIES M e and pull-back stages of the empty-cell treatMONTAN WAXCREOSOTETAR ACIDSERIES CN CREOSOTE MIXTURE SERIES WEe CRUDE OIL MIXTURE FREED CREOSOTE SERIES w l ment. Oils of lesser viscosity are removed ID I GRAMS CRUDE OIL 5 2 5 GRAMS WOOD TAR 328 GRAMS WOOD TAR NAPHTHALENE CREOSOTE CREOSOTE 4 2 9 GRAMS more completely during these steps. 9 9 GRAMS 22 6 GRAMS Further experiments at length developed a process which promises to be satisfactory. This involves the use of a toluene solution of the creosote to be examined, so that a full-cell treatment, such as was used 0 1 0 0 0 0 0 0 0 0 with salts, can be employed without lead1 2 3 4 5 1 2 3 4 5 6 ing to excessively large retents. In Figure 1 2 3 4 5 1 2 3 4 5 8 6 are shown the results over a period of 2 SERIES C 4 years of the exposure of six series of sapSERIES Pe SERIES CEe SERIES CG SERIES CG CRUDE OILEACHKEV SQUARE WATER GAS TAR WATER GAS TAR WATER GAS TAR WATER GAS TAR NAPHTHALENElings treated with toluene solutions of a SAMPLE 2 SAMPLE 2 SAMPLE 1 SAMPLE 1 ANTHRACENE REPRESENTS ONE 01 GRAMS 43.9 GRAMS 8.5 GR4MS 293 GRAMS SMALL SAPLING single creosote in graduated concentrations. RRRRR OSOUNO In this way, a gradation of retent is assured SUSPlClOUS which m a k e s for better uniformity and ;?%LTETACK better comparability. It also Serves to acSEVERE ATTACK celerate the test further, since some in0 SAMPLE REMOVED formation about the quality of a creosote 0 0 0 0 can be obtained in less than 1year's time 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 by observing its effects in low concentrat i o n s . Simultaneous experiments with OF SAPLINQ6 TREATED WITH SPECIAL OILS, FIGURE 8. FIELDEXPOSURE MIXTURES,ETC. larger amounts serve to afford f u r t h e r ~~
B
1
m[ 11
418
ANALYTICAL EDITION TABLE VI. Series Specific Kravity a t 3So/15O C. Benzene-insoluble, % niatillst,ion. . ' I
176-206 205-210 210-236 235-245 245-270 270-300 300-315 3 15-355 Residue above 355 Total Tar acids, 0-300' C % Sulfonation residue of 800-355" C. fraciion Diatillation carried t o 360° C. Domestic rreoaotes of foreign type.
'k
a b
44-55 1.095 0.09 0.43 1.30 0.31 2.12 1.39 9.35 16.37 10.81 35.91 21.97a 99.96 2.0 0.1
D 1.077
...
ANALYSES OF
COAL-TAR CREOSOTES
___
I 7n-2n.5
0,p
E,R
K
1.093 0.14
1.061 0.47
1T1D-IS
1J 1.059 0.25
1.060 0.38
1K 1.065 Trace
1M 1.068 Nil
0.53 1.38 0.35 16.61 9.26 12.85 6.98 3.16 12.44 36.31 99.87 2.5
0.76 1.70 0.36 4.63 4.53 11.10 8.97 5.85 23.19 38.83 99.92 3.6
0.36 0.43 0.27 19.39 10.73 15.34 11.34 5.87 17.36 18.86 99.95 5.5
1.21 3.44 2.68 23.31 7.52 11.80 5.81 8.12 18.49 17.43 99.81 6.4
0.00 0.24 0.62 9.17 9.01 16.49 12.30 5.36 23.15 23.12 99.46 5.6
0.00 1.56 1.35 11.02 6.58 13.46 11.79 6.66 24.57 22.74 99.73 5.9
0.00 0.71 0.69 8.00 5.91 12.23 12.30 6.04 20. so 33.06 99.74 11.3b
1.7
0.5
1.3
0.5
a. 1
0.9
1.3
TABLE VTI. ANALYSESO F WATER-GAS AND Series Specific gravity at 38O/15' C. Benzene-inaolnble, % Diatillation. C. 0-170
Vol. 6, No. 6
17-32 0.983 0.04
--33-431 Darta 1.037 0.50
2.14 1.96 2.83 30.14 9.08 16.18 14.91 5.47 10.64s 6.51 99.86 32.4
0.67 2.00 1.47 27.94 9.29 13.47 12.44 6.55 15.04b 10.68 99.55 8.3
3 Darts 0.999 0.06
205-210 210-235 235-245 245-270 270-300 300-315 315-355 Residue above 355 Total Tar acid!, 0-800' C., % Sulfonation residue. % of 300-355' C. fracti& 14.6 3.2 a A "regular" creosote. b Retort used in distillstion which wa8 carried to 360' C.
0.53 0.34 0.04 6.33 14.00 25.46 21.84 7.74
LOW-TEYPERATBRI
-.
L. T 1.011
0 1.015 0.04
...
1w 1.046 0.09 0.04 4.53 3.34 18.51 4.48 10.68 7.53 6.95 18.77 24.31 99.44 11.6'~ 3.2
TARCREOBOTEB 10 ._
1.020 Nil
. -.
1H
1L
1.021 0.07
1.018 0.16
7.34 99.78 25.0
1.28 2.11 0.36 15.99 14.39 30.03 16.27 6.30 8.48 4.69 99.90 0.7
2.47 2.56 0.49 9.03 4.74 13.99 9.18 7.20 25.41 24.82 99.89 19.2
0.00 1.05 1.71 12.74 11.15 23.00 14.96 5.32 11.77 17.29 98.99 Trace
0.00 2.63 2.43 12.62 14.42 21.09 14.07 4.71 13.66 13.66 99.29 Trace
1.76 1.12 13.70 8.95 21.44 14.46 14.60 6.02 17.54 99.59 0.3
11.5
0.6
14.8
3.0
1.0
3.6
16.16'J
TABLEVIII. ANALYSESOF SPECIAL OILS, MIXTURES,ETC.
0.00
Dreservatives from the standpoint of penna1.075 1.067 1.065 1.065 nence in poles. For this 0.02 1.11 3.98 ... w purpose it has g r e a t 0.09 I 1.24 0.65 0.88 0.43 4.65 0.29 1.83 0 promise. P e r h a p s it 0.10 m 1.78 0.10 1.12 will never be possible 6.60 15.03 5.39 35.83 11.60 P 7.03 7.64 13.14 to predict pole life in 19.63 a 11.74 14.53 21.63 absolute terms from the 13.98 7.56 11.69 14. 98a t0 6.09 3.40 4.36 .... .. sapling r e s u l t s , b u t 20.52 13.56 16.04 20.88 further experience may 33.66 39.05 9,875 99.92 ; 99.65 99.74 99.28 yield a more quantita0.3 e Nil 0.4 57.7a tive measure than we 1.5 0.6 8.6 ... ... 12.47 14.97 ... now have of the degree ... >600 >600 ... of acceleration achieved bv use of t h e saDliig. This s p e c i m i n preferred for general use in comparing the quality of oil is not well adapted to studies of methods of treatment or of preservatives. The six series referred to in Figure 6 give extent of penetration, factors which are known to be exexcellent evidence of the effect of quantity of creosote, as tremely important in full-size timber; nor can the results of do also series P and 0 included in the same chart and E and sapling tests be accepted with equal assurance with respect R in Figure 5. to the preservation of other timber than poles and posts. Figures 5 to 8, inclusive, show the results up to the present However, for the limited purpose for whioh it was designed time of numerous variations in the kind and quantity of the sapling test method appears to have a distinct field of preservative mixture. Some of these experiments have not usefulness. It is hoped that it will be possible to report further in a progressed far enough to be conclusive; others are somewhat impaired by the lack of precise control of quantity which year or two with regard to the results of continuance of the has already been mentioned. Nevertheless, the results exposures already mentioned and of others which have been shown in these charts and in Tables I11 to V, inclusive, are started more recently. At that time, a discussion may be believed to indicate clearly the possibility of distinguishing warranted of the significance of the results for the choice of between a good and bad preservative with considerable pre- preservatives. cision and in a much shorter time than is possible with an R E C ~ I V IApril ~ D 14, 1934. actual service test. Analyses of the oil preservatives used are given in Tables VI to VIII. The water-gas products RESEARCH on lithographic papers, carried on jointly by the mentioned in Figures 7 and 8 were kindly furnished for test National Bureau of Standards and The Lithographic Technical by reputable suppliers who vouched for their authenticity. Foundation for a number of years until July, 1933, when it was It should be borne in mind that the primary purpose of discontinued because of lack of funds, has been resumed at the the sapling test is to indicate the relative merits of various bureau under the research associateship plan. Series Specific gravity at 38O/15O C. Beniene-insoI:ble, % Distillation, C. 0-170 170-205 205-210 210-235 235-245 245-270 97n-2nn 300-315 315-355 Residue above 355 Total Tar acid8 0-300° C % SulfonatiAn reeidue '% of 300-355' C. frrtchon Coke test, % Float test, seconda a Distillation ceased a t 289' C.
F
M, X
. I
Iy
- . I I"-
Y
k
CG,CE
PG, PE
WT, WE
