INDUSTRIAL AND ENGINEERING CHEMISTRY
870
Vol. 24, No.
a
There remains the line reversal method of Kurlbaum (10) and Fery (6)which has been applied to the measurement of the temperature of continuous flames by several other investigators (Y, 9, 11). As a continuation of the present investigation, this method is now being applied to the measurement of the flame temperature in the engine cylinder. Preliminary results from tests over a limited range of air-fuel ratios indicate reasonably close agreement with the results of the radiometric method. Certainly the line reversal method is convenient and direct. The small size of the
0
,
en
M
160
120
CRAM A N G L i~DrsRC6.9. ~
FIGURE5. VARIATION OF FLAMETEMPERATURE AND PRESSURE IN ENGINECYLINDER WITH AIRFUEL RATIOOF 17.52:l
KO mention has been made of thermometric temperature measurements as applied to the flame in an engine. Two noteworthy temperature investigations with this method, employing a platinum resistance thermometer and thermocouples, respectively, were carried out a number of years ago (2, 3). However, the use of either a thermocouple or a resistance thermometer for the measurement of such rapidly changing temperatures as those encountered in the flame in an engine cylinder is open to some objection. TABLE I. RESULTS OF INVESTIGATION OF AIR-FUEL RATIOS MAXIMUM MAXIMUM TEMP. RADIATION TEMPERATUREW H E N Crank Crank EXHAUaT Galva- angle angle VALV~ nometer when when OPENS~ AT 120 AIR-FUQLTRIORETICALdetlec- mar. Aba. max. RATIO AIR tion occura temp. occurs A . T . C. % Cm. " A . T . C . " O F . ' A . T . C . O F . 9.55 63.0 10.25 26 3235 46 2716 11.14 73.5 12.45 21 3907 21 2428 12.44 82.1 12.88 31 5088 31 3555 14.10 93.1 10.82 31 5038 31 3695 15.27 100.8 7.27 41 4273 41 2849 17.52 115.6 7.16 51 3445 51 3240 a After top center.
I a
I
1
c . w K % a E w D%RCE=
I
'"
I 180
i
FIGURE 6 . VARIATION OF FUME TEMPERATURE AND PRESSURE IN ENGINECYLINDER WITH AIRFUELRATIOOF 14.10:l
FIGURE7. VARIATION OF MAXIMUM TEMPERATURE WITH AIR-FUELRATIO FulI line, measured temperatures' broken Iine caIcuIated temperatures of Goodendugh and BaLer.
measuring element which, in this case, is the sodium atom, removes the usual objection-that of time lag-to the thermometric method when rapidly changing temperatures are encountered.
CONCLUSION The agreement between the calculated temperatures of Goodenough and Baker and the observed temperatures of the present investigation is reasonably close for a narrow range of air-fuel ratios in the region of 90 per cent of the theoretical ratio. For rich or lean air-fuel ratios, the observed temperatures are considerably lower. The two principal sources of error in radiometric temperature measurements are the inaccuracy of the flame absorption measurements, due to their small absolute value, and the assumption of pure thermal excitation of the radiation from the flame. Both would lead to final temperatures which are too high. The error due to incorrect absorption should not exceed 5 per cent. At present there is no means of determining the error due to not having pure thermal radiation; but, since the observed temperatures are, for the most part, lower than the calculated temperatures, this error should not be excessive. LITERATURE CITED (1) Callender, Brit. Assoc. Committee on Gaseous Explosions, 1910 Report. (2) Callender and Dalby, Proc.Roy. Soc. (London),80,57 (1908). (3) Coker and Scoble, Proc. Inst. Civil Engrs. (London), 196, 1 (1913). (4) Fery, Conapt. rend., 137, 909 (1903). ( 5 ) Garner, IND.ENG.CHEM.,20, 1008 (1928). (6) Goodenough and Baker, Univ. Ill. Eng. Expt. Sta., BULL 160 (1927). (7) Griffiths and Awberry, Proc.Roy.SOC. (London),123,401 (1929). (8) Haslam, Lovell, and Hunneman, IND.ENO. CHEM.,17, 272 (1925). (9) Henning and Tingwaldt, 2. Physik, 48, 805 (1928). (10) Kurlbaum, Physik. Z., 3, 187 (1902). (11) Loomis and Perrott, IND.ENQ. CHIQM., 20, 1004 (1928). (12) Schmidt, Ann. Physik, 29, 998 (1909). RECEIVIDD March 3, 1932. Published with the permission of the Director of the Engineering Experiment Station of the University of Illinois. This paper is a preliminary report of an investigation carried on a t the atation
Drying Rates of Synthetic Resins with Drying Oils I. China Wood Oil CHIS. ALLEIVTHOVAS AND PAUL E. MARLING, Thomas 8i Hochwalt Laboratories, Inc., Dayton, Ohio
T
HE present investigation was undertaken to determine under various conditions (1) the drying rates of China wood oil alone, ( 2 ) the drying rates of China wood oil and resins. and (3) the effect of metallic driers mith and without small additions of phenols. It has been stated repeatedly in the literature ( 1 ) that the addition of phenols to China wood oil retards the> drying rate of the oil. This has been found true in >ome, but not in all cases during these experiments. The type of phenol employed and the conditions under which drying proceeds determine largely the results obtained with China wood oil alone. Contrary to the general belief, it has been found that commercially pure China wood oil dries faster with small additions of &naphthol under all the conditions tried except in indirect light, and here the drying time is not markedly retarded when the amounts of @-naphtholdo not exceed -1 per cent by weight. In most cases where 6naphthol has been added, the oil dries free from mat or gas check, in marked contrast to the drying of China wood oil alone. The effect of addition of small amounts of &naphthol to China wood oil varnishes has also been observed under varying drying conditions. Here the effect of @-naphthol depends largely upon the type of resin used in making varnishes. In general it may be said that the addition of small amounts of pnaphthol to varnishes formulated with resins of high acid value has a marked retarding effect upon the drying of the varnish film. K i t h the neutral resin varnishes, the addition of small amounts of @-naphtholusually speeds up the drying of the film. When metallic driers and 0-naphthol are both added to a varnish made from a neutral resin, acceleration of drying is more marked. Only n-ith unadulterated, commercially pure China wood oil is the drying effect of /3-naphthol observed. When other oils, such as linseed, soy bean, and perilla, are Idended with China wood oil, P-naphthol added in all cases markedly retards the drying of the resulting film. Under controlled conditions this mav offer a simple test for determining - the adulteration of China wood oil. DRYISGTESTS China lvood oil of cornmercia~purity, having a refractive Tvas used in these experiments. index of 1,5160 at 250 c,, The oil was heated to 260" C. and held a t this temperature until a one-inch (2.54-em.) string was obserwd when the oil was tested on a cold tin panel. The refractive index a t this point was 1.5080 a t 25" C. Mineral spirits was used as the thinner. The treated oil contained 62 per cent nonvolatile material. The metal drier was added in the liquid form, linoleates being used in all cases except as shown in Table I1 where the soligm driers were used. The liquid drier \vas added a t room temperature. The @naphthol and phenol were added to the oil after bodying and reheated a t 93" C. to insure complete incorporation of the phenol with the oil. The blank was always reheated with the tested samples. The varnishes were prepared by heating together the China wood oil and resin in the manner described above for China
wood oil alone. Driers and phenols, where used, were added to the formed varnish a t room temperature. The drying tests were made by flowing the film on bright tin panels placed at a 60" angle. KO effort was made to control the humidity. The drying end point was determined by touch, and the film was considered dry when no white mark remained after the finger Tvas drawn lightly across the film. For films that gassed or showed a mat surface, an exact drying end point was difficult to obtain. The indirect light came from the side and front of the films. The direct sunshine tests were made inside window glass. The mercury arc tests were conducted 18 inches from the source of light, using an 8-inch (20.3-em.) Cooper-Hewitt type tube. The electric oven was equipped m-ith an automatic temperature control. In all of this work the varnishes were tested within a n-eek after making.
INTERPRETATION OF RESULTS Table I s h o w the drying time of China wood oil with phenol and &naphthol under various conditions. It will be observed that 3.2 per cent of 0-naphthol added to the oil in all cases accelerates the drying of the oil. Eight-tenths per cent of phenol slowed up the drying under the mercury arc light, but 3.2 per cent did not change the speed of drying. Phenol does not retard the gas checking to the same extent as @-naphthol. TABLEI. DRYINQ TIME OF CHINAWOODOIL ASD @-NAPHTHOL ELECTRIC OVEK AT
hI.4TERIAL5
116' C.
Man.
PHEXOL
DIRECT B E L L DIRECT SUXLIGHTJ A R , SUXLIGHT
hrERCURY .ARC
INaIDE AT
.kIR AT
LIGHT 32-38' C. 27'C. Man. Hours Hours
15 15
35a 30 25 35 40a 35a
10 15 15
10 (I
WITH
OUTSIDE AT
21' C Houra
'
Gas check.
Table I1 records some drying times of China wood oil with driers and @naphthol. I n all tests conducted under indirect light, the addition of 3 per cent &naphthol to the oil plus the drier produces faster drying than with the oil and the same drier alone. In none of these tests does the addition of pretard the drying Of the Oil. T~~~~11. D ~ ~ - T~~~ ~ , - OF ~ cHIsA wooDoIL AND @-XAPHTHOL~ hf A T E R I 4LS Ch;n&o~;;d,~;\ o 2% lead and @-naphthol + 0 30 20% 6 7 cobalt
871
+
'~2$~~;~h;;~l +f+ o0.045% manganese 0 045'3% manganese a n d
INDIRECT MERCURYELECTRIC LIGHT S U ~ E H I VARC E LIGHT O V E ~ 27' C AT 38" C. AT 38' C. AT 116' C Man. Malt Mzn Mzn
AT
21Ob
301
2oc
3c
105 lOOb
30 155
15 15,
3 2c
60 420b
15 60t
15 30c
2 3c
3 0% @-naphthol 360 60 30 Percenta es of @-naphthol and drier baeed Ion a e i g h t of 011. 5 Gas chect Badly crimped
a
D~~~~~
3
I N D U S T R 1.4 L A N D E N G I N E E R I S G C H E M I S T R Y
812
Table I11 gives results of a study in indirect light a t 27" C. of the drying time of 100-gallon varnishes made with various resins, with and without the addition of &naphthol, and with and without drier. It is rather difficult in indirect light to get an accurate drying time of China wood oil alone, as the oil mats badly in most inside atmospheres. In the first column is shown the drying time of various resin-oil varnishes alone. A 100-gallon phenol-formaldehyde resin varnish dries faster than the oil itself and does not gas-check. All of the other resin varnishes alone gas-checked badly. The next two columns show the effect of addition of 2 and 4 per cent of @-naphthol. The effect in this case is not marked, but when &naphthol is added to the same varnishes with drier there is an acceleration in drying in the case of the petroleum-hydrocarbon resin varnish and with the oil alone. With the p coumarone resin varnish there is also an acceleration of the drying with the addition of @-naphthol to the varnish and drier. This is characteristic of P-naphthol with a neutral resin. TABLE111. DRYISGTIMEAT 27" C.
IN
INDIRECT LIGHT DRIER6 DRIERb
27% 8hfATERI.4LS
RL4NK
~ A P H THOL~
+2%
8-
4% 6NAPETHOLO
DRIERb
Hours Hours Hours Hours 120 120 120 (set)o (slightly (slightly 1.5 set) set) Petroleum-hydrocarbon 120 120 120 resind (set)c (slightly (slightly 1.16 set) set) 120 120 Modified phenol-formal- 108 dehyde resind (setjc (slightly (slightly 1.5 set) set) 100% phenol-formalde108 108 108 dehyde resind (set, (set, (set, 1.5 clear) clear) clear) p-Coumarone resind 120 120 120 (set)c (slightly (slightly 1.25 set) set) 120 120 120 Rosin esterd (set)c (slightly (slightly 1.25 set) set) Hardened rosind 120 120 120 slightly (slightly (slightly 4.5 ( sit)o wet)c wet)c 120 120 120 Kauri resind (slightly (slightly (slightly 2 . 2 5 set)c set)c set)c 5 Percentage of @-naphthol based on weight of oil. b Based on weight of oil; lead 0.170,manganese 0.005%. c Gas check. d 100-gallon varnish. China wood oil
TABLEIV. DRYISGTIMEAT
Win.
Hours
Hours
1.0
0.666
0.833
0.666
2.0
2.0
THOLa
THOLa
Min.
Min.
1.5
F'.
DRYINGTIME AT 38" c. LIQHT
USDER
MERCURY ARC DRIERb DRIERb
+2%
2 % 8-
MATERIALS
8-
4% 8NAPH- K ~ P H -
BLANK T H O L 4 Mzn. Man. 35. 30
THOLa
+4%
8-
XAPH- NAPH-
D R I E R b THOLa
.Win. Xzn. Min. China wood oil 25 30C 15 Petroleum-hydrocarbon resind 30c 30 25 15 15 Modified Dhenol-formal35. 30 30 25 20 dehyde-resind 100% phenol-formaldehyde resind 35 30 30 20 20 p-Coumarone resind 40.. 40 35 20 20 Rosin esterd 35 35 20 20 35c 35 Hardened rosind 40 40 40 35c Kauri resind 35 30 30 35c 30 a Percentage of 8-na hthol based on weight of oil. b Based on weight oPoil; lead 0.1%. manganese 0.005%. c Gas check. d 100-gallon varnish
THOL"
Min. 15
12 20
20 20 20 40 30
C. in an electric oven. I n this case the addition of @-naphthol
+2%
+4% N.4PRTHOLa
D R I E R b THOLa
Min.
1.5
N.4PH-
8-
TABLEVI. DRYINGTIME.4T 54"
10 30 30 25 25 40 60
Table IV gives the results obtained by drying the same varnishes in inside sunlight a t 38" C. Here the addition of 2 and 4 per cent of @-naphtholto the oil alone accelerates the drying. Likewise P-naphthol accelerates the drying of varnishes made with petroleum-hydrocarbon resin, 100 per cent phenol-formaldehyde resin, p-coumarone resin, and rosin ester, while it retards the drying of the other resin varnishes. When driers are used, the results are slightly different. The
c. IS ELECTRIC OVEN DRIERb DRIERh
+Win. Man. 10
15 10 180 390c 2 10 China wood oil Petroleum-hydrocarbon 10 180 10 resind 300 210 Modified phenol-formal30 150 20 dehyde r e s i d 105 150 100 % phenol-formalde20 30 180 210 hyde resind 390 25 200 20 210 Coumarone resin4 390 25 10 180 210 osin esterd 300 40 30 300 150 105 Hardened rosind 20 60 180 150 150 Kauri r e s i d a Percentage of @-naphtholbased on weight of oil. b Based on weight of oil; lead 0.1%, manganese 0.005% c Gas check. d 100-gallon varnish.
h'
T.4BLE
Table VI records drying rates of the same varnishes a t 54"
8-
4% 8NAPH- NAPH-
BL.4NK
h*APH- N.4PHT H O L a THOL'"
addition of small amounts of P-naphthol with drier speeds up the drying of the oil alone, but among the varnishes tested it is only in the case of the petroleum-hydrocarbon resin varnish that the drying rate is not retarded by addition of P-naphthol. Table V shows the drying rates of the same varnishes under the mercury arc light a t 38" C. The oil alone and all varnishes under this condition are accelerated by the addition of 0naphthol to the varnish, with the one exception of the limehardened rosin varnish. With the drier and @-naphtholthe drying of China wood oil alone and the petroleum-hydrocarbon resin varnish are accelerated, while @-naphtholwith the other varnishes shows either a retarding action or no effect at all.
does not show any marked effect except on the lime-hardened rosin varnish, where there is a marked retardation of the drying. With the addition of @-naphthol and drier to the 1.0 1.0 varnish, the drying is accelerated in the case of China wood oil alone and also in the case of a petroleum-hydrocarbon resin 1.5 1.75 varnish. The drying of the rest of the varnishes is retarded by the addition of fi-naphthol, except that a varnish made 5.0 5.0 from neutral p-coumarone resin is not affected by 2 per cent of @-naphthol,but the drying is retarded by the addition of 2.25 2.25 4 per cent of 6-naphthol. Larger amounts of @-naphtholwith China wood oil alone have been observed up to 15 per cent by weight of the oil. There is not much additional acceleration in drying with more than 4 per cent of @-naphthol. However with the varnishes, addition of more than 4 per cent 38" C. IK INSIDESUNLGIHT of P-naphthol usually retards the drying when the proportion of metallic drier is kept constant. DRIERb DRlERb
2% 8-
MATERIAL@
+4% 8-
Vol. 24, No. 8
bf.4TERIALS
2 % 8-
4% 8-
NAPHTHOL~
s.4PHTHOL'
BLANK Hours Hours Hours 30 (set) 30 (set) 30 (set)
China wood oil Petroleum-hvdrocarbon 30 (set) 30 (set) 30 (set) resinc Modified ohenol-formal27 25 10 24 30 24
24 30
24
30
+2%
8-
+4%
8-
h-APH- N A P E D R I E R & T H O L ~ THOL"
Min. 8
Min.
Min.
5
5
8
5
5
8
15
20
10 8 8 30
12
15 10 20 60 30
8
:g
30 30 (set) 30 24 (set) 8 12 15 24 30 24 a Percentage of &naphthol based on weight of oil. h Based on weight of oil; lead O . l % , manganese 0.005%. c 100-gallon varnish.
Table VI1 shows the drying time of petroleum-hydrocarbon resin with China wood oil varnishes of various lengths in indirect light with the addition of @-naphthol and phenol. The petroleum hydrocarbon resin referred to is produced by the polymerization of unsaturated hydrocarbons such as are present in certain fractions of cracked distillate. The resin
I N D U S T R I A L A X D E N G I N E E R I N G C H E 31 I S T R Y
August,' 1932
is practically neutral and nonsaponifiable and is unsaturated in character; the resin used in these tests has an iodine value of 135 to 140. It may be noted that the addition of 0naphthol greatly accelerates the drying of long oil varnishes and has less effect as the lengths are shortened; a 12-gallon varnish showing no acceleration in drying. The effect of phenol is less marked than that of 0-naphthol. TABLETII. DRYISG TIME O F PETROLEUM-HYDROCARBON RESINTARSISHES IS INDIRECT LIGHTAT 27" C. METAL METAL METAL LEXQTHSOF CHINAWOODOIL DRIER DRIER DRIER VARNISHES WITH PETROLEUMMETLL 1.5% 3% 3% HYDROCARBOX REsIN DRIER&&NAPHTHOLE-N LPHTHOL P H E N O L Gallons Man Mzn .Ma n Man. China wood oil SO b 30 30 60b 1000 906 40 40 606 100 60 40 40 60 50 45 35 36 40 25 40 30 30 40 12 40 40 40 40 a Percentages of drier and phenol based on ueight of nonvolatile; lead O . l % , manganese 0 005% b Gas check.
+
+
+
873
added. The same general acceleration as with lead and manganese is observed. From the above results it is apparent that under certain conditions China wood oil dries faster with 0-naphthol. I n another publication it is hoped to study the effect of the addition of &naphthol to linseed oil and other drying oils. Rogers and Taylor ( 2 ) have pointed out that phenol inhibits the oxidation of linseed and China wood oils. It is generally accepted that China wood oil dries both by oxidation and polymerization. In the case of China wood oil it may be possible that @-naphthol increases its rate of polymerization. SU.\IMARY
1. The drying of commercially pure China wood oil is accelerated by small additions of 0-naphthol when the drying takes place under mercury arc light, sunlight, and a t elevated temperatures. 2. Synthetic resins markedly influence the rate of drying TABLEVIII. DRYISGTIMEOF CHIR'AWOODOIL TARSISHESof China wood oil, and the rate of drying of China wood oil WITH VARIOUS RESIR'SAND COBALT DRIER varnishes is largely dependent upon the type of resin used. (Length of varnishes, 100 gallon) 3. China wood oil varnishes made with natural or synIlDIRECT INSIDE BELL BELL thetic resins may or may not be retarded by 0-naphthol. In LIGHT, SUNLIGHT, J A R , JAR, 38O C O X Y Q E N AIR 27' C . general, the drying of neutral resin varnishes is accelerated by JIATERIALS Hours Min. Hours Hours the addition of 0-naphthol, and this effect is cumulative when China wood oil + cobaltG 2 15 1.5 2.5 0-naphthol is used in conjunction with metallic driers. Rosin-ester varnish + cobalt 3.5 20 3 (slightly 2 . 5 W.tl
Modified phenol-formaldehyde 3 resin varnish cobalt 100% phenol-formaldehyde resin 3 varnish cobalt Petroleum-hydrocarbon resin varnish cobalt 1.5 p-Coumarone resin varnish 3.5 cobalt a Cobalt, 0.017% b y weight of oil.
15
+
+ +
20 15 20
+
2.5
3(diFg"htiy wet) 3 (slightly set)
2.5
2.5 3 (slightly set)
1.5 2.75
Table VI11 shows the drying of China wood oil and 100gallon varnishes made wit,h various resins with cobalt drier
LITERATURE CITED (1) Morrell, R. S.,Paint Varnish Production Manager, 36, No. 7, 12-17 (1930). ( 2 ) Rogers and Taylor, J . P h y s . Chern., 30, 1334 (1926). RECEIVED April 7, 1932. Presented before t h e Division of Paint and Varnish Chemistry a t t h e 83rd Meeting of t h e American Chemical Society, New Orleans, La., March 18 t o April 1, 1932.
Synthetic Lignin L. F. HAWLEY AKD E. E. HARRIS, Forest Products Laboratory-, Madison, Wis.
I
N' 1931 Hawley and Wiertelak ( 1 ) reported the chemical analysis of wood that had been subjected to a temperature of 135" C. for several periods of time up to 8 days. The analysis showed a partial decomposition of carbohydrates in the wood and the formation of a material (roughly equivalent in amount) that was isolated along with the lignin. I n order to investigate this lignin-like material farther, it was prepared from Cross and Bevan cellulose and was thus obtained unmixed with the lignin of the original wood. The results of that investigation, confirming and extending the previous work, were presented a t the spring, 1931, meeting of the . ~ I E R I C A N CHEMICALSOCIETY,but tht.y were not published because meanwhile Sherrard and Harris ( 5 ) and Ritter, Seborg, and Mitchell ( 3 ) had shown the possibility of serious error in the standard method used for lignin determination. Instead of publishing, the researchers decided to repeat the experimental work, using the improved method for deterniining lignin. Only the parts of the data from the first experiments that are required for comparison will be presented here.
HEATTREATMENT
OF
CELLULOSE
I n the present experiments large quantities of Cross and Bevan cellulose were prepared from white spruce and sugar maple by the method used in isolating the cellulose for its
quantitative determination. Fifteen-gram samples were sealed in glass tubes and heated in a pressure-steam retort for 1, 2, and 8 days a t 135" C. Duplicate runs were made, and, except in the few instances where a tube was broken accidentally, the figures in the table are the averages of two closely agreeing determinations, one from each ddplicate tube. The slight gas pressure remaining in the tubes after cooling was relieved by breaking a n end of each tube under water, and an approximate determination of the gas evolved was made. This gas was largely carbon dioxide, but under the conditions of the experiment no significant quantitative figure could be obtained. The amount of water formed during the heating can be calculated approximately from the difference in moisture content of the samples before and after heating. The data in Table I, when considered alone, indicate that the rate of the reaction with the spruce was much faster than with the maple celluloses, This difference, however, is probably caused by something else than inherent differences between the species. In the previous work a maple cellulose, prepared and treated in as nearly as possible the same way, gave 18.8 per cent lignin in 8 days, while the softwood cellulose (loblolly pine in this case) gave only 11.2 per cent. With any one lot of cellulose the rate seems to be the same in all runs, as is shown by the relation between period of heating and extent of reaction, and the close checks in duplicate runs: but with different lots of cellulose the rates inay be very
