Document 50xvGXVXEM5m6n4Ne1QwY3B8

Report Number: Indexed Pile: 1865 ESR-68-43 Distribution on last page RlfllliCI COPY HOT TO SI TAIEH ROM UBRAgY E. I. du Pont de Nemours & Company P & F, Research Division Experimental Station Laboratory ^ Research Report IMPROVED PIGMENT GRINDING ,! C 1 i.D V 1. Vibration Assisted Mill Base Preparation 2, SoniCo's Orboresonance Technology Date Issued: Period Covered: Project No.: Previous Reports Notebook No.: October, 1968 April - August, 212009 None 379E, 40?E 1968 PREPARED APPROVED BY A. W. ANDRESEN When this report is no longer needed, please return it to the Pile Room, P & P Dept., Experimental Station. pM. mJU TABLE OF CONTENTS Page INTRODUCTION............................................... .......................... ..,.................... 1 OBJECTIVE........................................................................................................... 1 SUMMARY AND CONCLUSIONS.................................. 1 PATENT STATUS.............................. 3 ACTION TAKEN OR PROPOSED. .. 1........ ..................... ............. ............. 4 ACKNOWLEDGMENTS...... .................................. 4 DISCUSSION.......... .. ............................................... 5 1. Application of Vibration to Various Mill Base Grinding. ........................................................ ............................. ... 5 a. 913-560 "Harmon" BlueMill Base...................................... 7 b. 901-550 Monastral Blue Mill Base...... ........... .. 9 c. 907-686 Chrome Yellow Mill Base.......... ......................... 10 <U' 907-582 "Milori" Blue Mill Base................................. .. 10 2. Orboresonance Technology............................................................ 11 REFERENCES.......... .................................................................. TABLES 1-4 FIGURES 1-10 APPENDIX ABSTRACT DISTRIBUTION LIST l4 DUP030012951 INTRODUCTION The purpose of pigment grinding is to incorporate pigment into paint vehicle to obtain a-fine particle dispersion. According to Patton (Ref. 1), this process is carried ,out in three overlapping steps. They are wetting, grinding and dis persion. Wetting refers to the displacement of air and moisture in the pigment by other .constituents of the mill bases. Grinding refers to the mechanical break-up of flocculates and agglomerates. Finally, dispersion refers to the permanent particle separation. This work is concerned with the second step whose successful execution is a prerequisite to a well dispersed mill base. OBJECTIVE Our commercial objective is to develop grinding techniques that yield ball mill, two-roll mill and flushed pigment qualities at loiter cost by adding resonance vibration to the present 47 process. Our immediate technical objectives are to establish the effect of (1) adding vibrational energy to sand mills and (2) using denser, harder media than sand in the 47 process. SUMMARY AND CONCLUSIONS The scope of vibration is normally defined by stating amplitude and frequency. Another way is to specify acceleration and frequency. The experiments described in this report (Figure 4) were carried out at relatively low G* (13-18G) acceleration and average frequency (40-60 cps). This is in contrast to the Soni-Co's capability (Ref. 2) which Is 150-480G at 60-350 cps. Presently, SonlCo Is fabricating a modified sand mill at our request. The purpose of our experiments, therefore, was to obtain some evidence of improvement via vibration assisted milling using available equipment. *1G Gravitational acceleration ** 386 (in./sec.2) in vibration terminology. DUP030012952 2- - The available equipment consisted of a wide frequency range oscillator-amplifier""electromagnetic driver we have borrowed from the Engineering Technology Laboratory. With this set-up* we have examined five different mill base systems. Of these* the Harmon Blue system was chosen for a detailed analysis. 913-560 Harmon Blue The experimental results with 913-560 copper phthalocyanine blue mill base show a marked decrease in seeding as measured by gloss measurements (Figure 1). To substantiate this finding* electron micrographs of the mill base cross sections were prepared (Figure 2). It is apparent that the unbaked mill base surface preparedrwith vibration is smooth while the surface of the control mill base without vibration is rough. The degree of flocculation determined by electron micrographs of the crosssections (Figure 2) were about the same. In addition* we determined tinting strength and L, a* b Adam's color coordinates. The results show increasing tinting strength with vibration (Figure 5). The Adam's coordinate changes calculated from the ttColormastern reflectance measure ments also indicate that the mill base prepared with vibration Is bluer than the control sample (Tables 1* 2). The scanning of important variables for this system was done by performing a factorial experiment. The Yates' method of analysis (Ref. 12) showed that, in addition to vibra tion, the effect of (sand/mill base) ratio and % solvent in mill base are important. The (sand/mill base) =1.5 was found to be optimum for this system (Figure 6). In every electron micrograph including Flint's let down sample, we found dense agglomerates that are not completely wet (Figures 2* 5). Similar particles were observed in the case of 901-550 Monastral Blue G (Figure J) DU P030012953 3- - High spot experiments to-assess the effect of grinding media were also performed. Of the three different media used, only steel shot showed signs of improved gloss (Table 3> Figure 9). Other Mill Bases Four other systems examined are 907-686 Chrome Yellow, 907-582 MMi`lori" Blue, 901-6253 Black and 868-550 Monastral Blue. A reasonably detailed examination for each of the above systems was necessary to select a proper system since either too easy or too complex a'system might not reflect the effects of the low G orboresonance. The results are summarized in. Table 4. Mill base samples of Chrome Yellow in particular were., sent to G. Orvis of Flint Development Laboratory. He concluded that the mill bases with vibration (Figure 4)- possess higher tinting strength and cleanliness (Ref. 3). These two properties, however, were not reflected in the electron micrographs (Fig. 8) which showed excellent dispersion.in both cases; indicating, the dif ficulty of defining such properties as cleanliness and transparency. Orboresonance A working knowledge of orboresonance vibration was gained by .visiting SoniCo laboratory (Ref. 2). This knowledge was essential in calculating-the performance of MB Electronics electromagnetic, variable frequency oscillator system (Ref. 4),. Required mathematics with worked out sample calculations were carried out to analyze our experiments. Detailed description of the hardware and the measuring techniques will be reported later along with actual experimental results at SoniCo, PATENT STATUS Most of the patents on orboresonance belong to Bodine Soundrive Company. SoniCo, Inc., which is the subsidiary of Shell Oil, also owns some patents and has an agreement with Bodine Soundrive to use its technology freely. Du Pont in turn has a working contract with SoniCo and Bodine Soundrive to DUP030012954 4- - utilize the art. A detailed agreement can be obtained from B. M. Sturgis of Orchem, A voluminous patent study- on the subject has been made by R. D. Morse of Engineering Department (Ref. 5). A Notice of Invention on the vibration assisted milling based on our findings up to date will be written by ll/l/68^, ACTION TAKEN OR PROPOSED Based on the findings contained in this report, the SoniCo*s proposal to fabricate a orberesonance assisted model sand mill was adopted. The proposed fabrication time is four weeks. . Chrome Yellow mill base prepared by our early crude experiments were evaluated by G. Orvis of Flint. We will send another sample which is ground with our improved equipment by 9/15/68. ,,Harmon,, mill bases will be sent to W. Moon and S. Arora for their evaluation. We expect to obtain-'their appraisal within a month. ACKNOWLEDGMENTS I would like to thank N. Komodromos, W. Bullock, W. Balloon, S._ Arora/ G. Orvis, W. Moon and J. King of Flint for their help. The assistance of W, Callahan of Philadelphia Process Development, D. Troy of the Experimental Station, and J. Lamiet of Pigments Dept, is appreciated. L. Lennart of Marshall Laboratory helped to expedite the computer calculation. DUP030012955 5- - DISCUSSION 1. Application of Vibration to Various Mill Base Grinding Breakdown of F & F mill base production indicates that approximately 70# of the total production is processed via 4-7, 48 and 49 processes (Ref. 6). The remaining 25# is ball milled while about 1# of very difficult-to grind pigments go through two roll mills. Cost-wise, typical milling cost ratios of these different treatments for automotivejgrade lacquer shows 47 process/ ball milling/2-roll milling//l/l*75/S*5* We can, therefore, cut down the mill cost considerably by'enlarging the scope of sand mill usage. < Another incentive for this project was pointed.out by1 FitzGerald who recognized the importance of deagglomeration in controlling the degree of flocculation by means of AB type dis persant (Ref. 7)* More specifically, he suggested the use of orboresonance technology and. harder grinding media. Du Pont has a detailed agreement with SoniCo to exploit this technology ,, (Ref. 8). Harder grinding media such as "Zireoa" and steel shot are available from Quackenbush Company. A few exploratory experiments, however, immediately uncovered the need to: find proper candidate mill base system for testing which can reflect the effect of superposed vibration on normal sand mill operation' and # select proper methods of measuring the mill base quality. Hegman gage, for example, was too crude for all the systems we have examined. Observation of a Brownian motion in a dilute system has also been used extensively, but its relation ship to the dispersion stability of the real, concentrated system is not defined clearly. To select a proper system, we consulted the Flint dispersion group who supplied the following list (Ref. 9). DUP030012956 6- - Mill Base Systems Group I (47 Process) 907-686 (2 pass) 907-808 (2 pass) 907-804 (2 pass) 907-131 (1 pass) 907-630 (1 pass) 907-393 (1 pass) Pigment/Vehicle Heed For Improvement Chrome Yellow// MMA/DEAM Monastral violet "Thiofast" red lake Ti-Pure white Ferrite yellow Monastral yellow One pass desired. -' *1 it Improved tinting strength 11 11 ii Less grit, lower fineness ti ti 11 ii Group II (Ball Mill) 907-582 901-6255 "Milori" Blue Peptized carbon black/MMA Improved seed/stability Improved tinting strength Group III (2-Roll Mill) 901-3393 901-5804 Monastral maroon/ MMA "Thlofast" red lake Extreme grit ri 11 Group IV (under development) W-56O -816 W-678 -684 "Harmon" blue// MMA/AH Monastral Maroon B 3RLT "Irgazin" yellow Monastral Orange Develop as 47 process 11 ii 11 ti n 11 it ti 11 n 11 ti The above list indicates areas where research is needed in terms of technical difficulty. I have also consulted a list which contains information on usage volume and per pound price (Ref, 10). The results of reasonably detailed experiments (Tables 1, 3 & 4) indicated that the "Harmon" blue system of Group IV is most suited for our study. DUP030012957 7- - a. 913-560 "Harmon11 Blue Mill Base This 913 line dispersion based on Allied Chemical's "Harmon" blue chlorinated copper phthalocyanine pigment is produced for 944-, 9^5- line automotive refinish* The sprayed panel differs from the regular copper pht^l^cyanine blue (W-550, for example) pigment.", in its greenish flip-flop when viewed from the side. As the electron.micrographs show (Pig. 2), the system exhibits large areas of flocculation plus some foreign material (Pig. 3) which is not wet completely by the liquid portion of the mill base. Our Initial guess on the identity of the^e dark particles was that they might be sand fragments. However, the presence of this"material in the mill base ground with steel shot (Pig. 9) seems to contradict the supposition. Similar particl^i^were observed in a system where we used Du Pont' s Monastral- blf|| phthalocyanine blue (Pig. 7). Pigments Department thinks that*they might be small impurities of aluminum sulfate, sodium sulfate or sodium carbonate (Ref. 11) which are used to grind theJuried pigment filtrate. The 913-560 mill base prepared according to the, 4? process exhibits a large number of seeds. These seeds are readily perceivable visually as small dots when viewed from the side. Under optical microscope (100X), the seeds appear as small mounds. Currently, we are attempting to take electron micrographs of the cross-section to see -what is underneath. These mounds, of course, tend to lower the gloss due to the decreased specular reflection. And, since the gloss measure ment is relatively quick and reproducible, this method was ideal to cheek the effect of vibration. As will be discussed in detail later, the level of vibrational energy used in experiments described in this report is an order of magnitude less than what is realizable in SoniCo's orboresonance equipment. Therefore, until SoniCo gets ready to perform more meaningful experiments., we decided to examine other variables as well. More specifically, we examined the effects of vertical vibration (Pig.4, see section on orboresonance), (sand/mill base) ratio, quantity of solvent, "blade geometry. DUP030012958 A schematic diagram of the vibration assisted 47 process set-up is sketched below. To drill press General Radio Corp. Oscillator (10-100,000 cps,) (See Figure 4 for actual photograph) The mill bases thus obtained were doctor-bladed onto glass slides and examined for gloss and ,,Colormastertt readings (Table 1). The measured values were then'analyzed by Yates1 method (Ref. 12) to' define important variables. It was found that the following variables, shown in. the order of effect, had marked influence on mill base quality, (More\ /Vibration +\ /Propeller \ . (r,. \ . / More \ (sandJ ^ (more sand ) ^ (type bladey ^ ra onJ > (solvent J Based on this finding, we decided to examine the effect of batch grinding time when the 47 process is carried out with vibration and with more sand (Figures 1 & 5). In Figure 1, ten minutes grinding time is nominally equivalent DUP030012959 -9- to a single pass in continuous operation. It can be seen that the 20 gloss of the-test case is nearly twice that of the control. This finding is also reflected in the surface rough ness depicted in the electron micrographs (Figure 2). The pictures, however, do not reflect marked reduction in the flocculated area. We hope this will be the case when an orboresonance of large magnitude is applied. In addition, we also examined tinting strength by mixing 5 parts of mill base with 95 parts of 926-9377^ white. The mixtures were doctor bladed onto the black ceramic panels. The tinting strength then was compared in terms of the green fleetance (Fig. 4, Table 2, Appendix). Yates* analysis again showed that vibration alone or vibration with higher (sand/ mill base) ratio gives better quality mill base. The effect of grinding time is shown in Figure 4. b. 901-550 Menastral Blue Mill Base Chronologically, this was the first mill base we iinr tried. This copper phthaloeyanlne blue differs from the "Harmon" blue in that its sky blue color does not contain -the greenish , tint. Unlike "Harmon" -blue, it also did not have any seeding problem, and the degree of flocculation was much less pronounced (tg. 7). In this case, the vibrational energy was also introduced by shaking the can horizontally by using the "Yibromixef" which was available from PLE. Attempts were made to analyze the result by viewing the diluted mill bases with 56OX optical microscope. But with this method, the difference between the mill bases prepared with and without vibration could not be differentiated. We also letdown this mill base according to 868-0550 formulation to determine hiding power by preparing wedge sprays. Again, the mass tone color was rather deep and did not show the effect of vibration. DU P030012960 -10- c, 907-686 Chrome Yellow Mill Base Of all the systems tried, this lead chromate mill base was by far the easiest to grind. In fact, even the raw mill base without any sand grinding exhibited Brownian motion under optical microscope. This is reflected in the electron micro graph of the mill base cross-section (Figure 8). The mill bases prepared with horizontal vibration, however, were sent to G. Orvis of Flint for-Ms evaluation. He concluded that vibration was beneficial in obtaining higher tinting strength and cleaner color. Our analysis verified his findings as shown below. Reflectance readings, are shown in Table 4. Panel Control 1 Control 2 With Vib. at 60 cps. With Vib. at 150 cps. Adam*s Color Coordinates La b' 93.69 91.19 -8.02 2.98 56.02 51.54 90.21 90.04 2.94 2.96 54.55 54.79 We also subjected this mill base to ultrasonic vibration (20,000 cps.), using-R. Prugh's equipment at Jackson Lab., Orehean. Again, the optical microscope observation showed little difference although the settling rate of the sample with ultra sonic vibration was markedly slower than the control. d. 907-582 wMilorin Blue Mill Base This is the ferric-ferrocyanide mill base which is normally ground in ball mills. In this study, however, we used 47 process with and without vertical vibration. The effect of different kinds of grinding media was also studied (Table 4). It can be seen that change of sand to steel shot, "Ceramedia" glass slags and "Zircoa" Zr02 gave pooer results. Vibration at 50 cps., however, seemed to improve the situation. DU P030012961 -11- In general, however, the seeds observed in all the runs were so severe that none-f the variables seemed to have any effect. We, therefore, changed our emphasis to the Garmon" blue system which showed much less degree of seeding. 2. Orboresonance Technology The word, orboresonance, describes the response of a system with elastic element to a cyclic, oscillatory force. The response is characterized by large amplitude at high frequency. In the ease of nonresonating system, the amplitude decreases considerably as we increase the frequency (Fig. 10). The starting point to deduce the above statement is the well known governing equation of the mass-spring-damper system shown below subjected to sinusoidal forcing function (Ref. 13). - .aw ** m d*x ^ dta + C cbc dt + kx = F0 sin wt (1) I Fo sin wt DUP030012962 12- t = time x = displacement w =* oscillation frequency in radians c * dampening coefficient k spring constant of the elastic element m mass of the system in lb./(in./sec.) units PQ maximum amplitude of forcing function The right-hand diagram shown above depicts the model of our sand grinder with some hypothetical numbers for the purpose of illustration. An elementary solution of the governing equation gives? Amplitude o responding system / F,,/K * (f>* Plot of equation 2 is shown below. nm If we do not have an elastic element, (k = o), the above equation becomes: DUP030012963 13- ^ = Wm2TM2 + cE Therefore, if in is large, X becomes small unless FQ is very large. freq. The actual measurements of our experimental unit are shown in Figure 10. It can be seen that the natural frequency of the system was found to be at 30 cps. which is too low. One way to get around this is to increase k which means a stiffer spring, which in turn requires a stronger oscillator to drive the system. The acceleration, measured in terms of G unit which is 386 (in./sec.2), can be obtained from the following rela tion which can be easily derived. dax g (acceleration) = * -(2-rrf) x (4) where f * frequency in cps. By measuring amplitude and frequency, therefore, the G forces can be computed. The calculated G forces for our system showed that our unit can generate 18 G at best (Fig. 10). DU P030012964 14- The present unit, therefore, is a rather feeble device compared to the SoniCo*sl00-50Q 0, 50-550 cps. -unit. All-arrangements have been made to run the experiment at SoniCo within two months. To describe the resonance vibration more fully, one also needs to know the method of determining dampening coefficient, power consumption and Q calculation which determines average energy stored per energy throughput per cycle. I have learned these techniques during my visit to SoniCo. Details of these calculations will be described in the next report along with the actual orboresonance experimental results. REFERENCES 1, Patton, T. C,, Paint Flow and Pigment Dispersion. Interscience Publ., 1964. 2. Ahn, Y., Trip Report - SoniCo, Inc., A Subsidiary of Shell Oil Co. - Orboresonance Technology, File: 1870, `July 2, 1968. 5. Orvis, 0., private communication, July 23, 1968. 4. MB Electronics, 2120 MB Amplifier - EA1250 Exciter,. New Haven, Conn. 5. Morse, R. D., Orboresonance Generation and Utilization of Vibratory Energy, Ace. No. 13047, Engineering Dept., April, 1968. 6. Baker, L,, F & F, private communication, April 22., 1968. 7. FitzGerald, E. B., Research Backlog Proposal No. 67-15, Improved Pigment Grinding Technology, 8. Sturgis, B. M., Orchem Patents Ss Contracts Division, Seminar on Orboresonance Energy, August, 1966. DUP030012965 -159. Orvis, G* , Balloon, . and Moon, W., F & P, Flint, private communication, March, 1968. 10. FitzGerald, E. G., Letter to A. W. Andresen, Flushing as a Route to Deagglomerated Pigment Dispersion, File: 4835* February, 1968. 11. Gyorgy, H, H., Pigments Dept., Newark, N. J., private communication, August, 1968. 12. Davies,-0. L., The Design and Analysis of Industrial Experiments, Hafner Publ. Co., New York, N. Y. (1954). 13. Thomson, . T., Vibration Theory and Applications, Prentice-Hall (1948). 14. Manley, R. G., Fundamentals of Vibration, John Wiley (1942). YA/rsh 10/1/68 DUP030012966 FACTORIAL DESIGN WITH 913-560 SYSTEM TO DETERMINE IMPORTANT VARIABLES YA/rsh 9/24/68 o j in in HHW ^ CO <fs O CM CM K\ CM CfM-NOWVO vNo ON O ON On CM KN CM CM vo N* g o in - b in co ON OV ON CO CM CM CM CM t- -=t in o ON KN KN H ON ON o KN CM CM KN in ON-=t O VO 00 OCM -st o H in-sfr o n co vo k n OONH ON UN t- CM rH -st vo in -5F St nru CD ON O O k n k n -SF O O ON O st -Sr k n -sf ON ON ON ON , KN KN KN K\ * CM kOnn On o P(0 au CM VO tv O K\VO O H 0 fc- KWO -st Q VO CM > N-VOo ino H4- oinoH 01 ON f O ON VO CM in^. eO*OH st in in in in in in in vo vo n o Co VO VO vo VO vo vo vo io vo -st .st in vo vo vo vo rH in-St t- VO VQ CO KN H VO invo tv vo fr-VO CO -d* vo vo mvo o n co mvo tnvo tv in ON H 00 CM O H KN o in CM I KN KN CM CM H most N- KN KN UN H CM KN CM cH VO CQ CM VO KN VO KN CM <V H CM vo u n c m f~ VO in O KN H W AH rOH >fc CO O ON KN 00 UN fc-op KN KN KN CM KN KN 00 *st VO ON VO UN KN CM KN KN KN UN ON VO O ON CO CO ON CM CM CM CM UN KN VO VO 00 KN KNCO CM KN KN CM a d S' t H 0 II Ct^M-=UNt 8I fr, 6H O O CM KN UN UN UN in It O I iH l UN in i in i *0 OS H eO <V rH P rH rH 0* Ph Ph Oh IO 04 & fa 04 fa fa fa fa fa fa fa fa P Hdo>O> rH O &_ sw S5 _ 5 5W O>* ow' S5 SC 03 CM W.NR.'JfcW. S SR >g. oooo 4 S5-JK O O to H >H foe ao iod h KN C KN l rt & tv O q -=r Pp o P o Om "Q at ,o n o *0 0 0 POP p H * *H *0 o O 'P *4 o O 4O4 rH CM KN -=t UN VO t-00 ON O H CM d o drH U0 Vi st K1N O "S 4oo 03 DU P030012967 EFFECTS OF VIBRATION AND (SAND/MILL BASE) RATIO ON TINTING STRENGTH _________ AND COLOR PARAMETERS FOR 913-560 BLUE M ILL BASE1___________ w < m 03 0) bfl d (0 xx o x> < 0) -p (0 a H n u o <0 o< o ra S <0 'O <M 1-3 <J o m in VO in =t o o oH m e t 00 m =t it H o o o oP i 1+1 00 *--1 o > in 00 CM o in oo o oo ++ 1 in m t- K\ c m P VO o ooO B i f 1 in 00 o o 00 o it CO H i--i CM - P KS m it VO m o oH ti1 in IN- O i o\ GJ O K> rl P CM it 4 : o O OO i 4* + + 00 m o i Ov in o | in CM H 1 m 00 o 1 iH H rH S <U CO o o o m m K\ in o 03 2 CO r| H H rl H H H CM (0 CO <o <0 da **--i -1 ou EH 0 dC rl e in o H dd d H H H aa & in P in o H C c H ' H sa tn in r-l P Pc a in pH P d (0 o <0 <0 cd i i1 o oo in in in iS 8 1 m w o ofcr fcr tv- it iF it d o hD r-t dp P 03 o O d Xt IH CO O p P U p 0) u Oc O 0) < 3 O d CO a> P c HO CO H CQ c Sc ft (U S5 u pa CO rl bD 3 H O) a p O P <w o j h P XS co x: 3 bO U *H O (4 CO 3 *o CQ x t> u SH >> CO co x: i--1 d 1-3 < K>> II P CQ x: 'O P cd a Pd w S 14 cd cO <S P 0) p XJ P X2 taO CO cO P p O CO a o ft V p 0) (U 4 0> ft x: JH <3 > t 3 cC H it Sh n CO it cd x; CM 3 P i4 o o CM IH O rH op Q o S IH d at rl Eh 0) o a p u CO > o CO CO CO P p Eh 55 H CU CO 00 x:vo ca\ St in >vxu >* o\ DUP030012968 TABLE 3 The m ill bases were ground fo r 30 min. a t 2000 rpm. Samples adjusted to 35!% by adding Lucite solvent Smaller value indicate high tin tin g strength. 4-> C o oo u cp oo o P 0) aC> T<oJ I -t at G. x: -aP> o p H o -p s fcft. in <o*4 C<wO, H CQ <H i-Q Q pj @ H52 S CU !=> w i4 O SM = zo s ZO SB miv--t amM 0\ J> oo & M s s w n bfi fCt 0a) CD P T<J8 c5 CD - T3 CD CD CPO BJ cd a t, Ho O CD O Si H pq St CM O CM VO S rH m ms. ViOn C(0Q o oo t>~ I--f O CCMM Cr-Mt o COV1 Tf3t r-i Vi 0 01 M. i IS t imn x> oa> >H tt XI > zO -=t s CoM COM CmM CoM -V=Qt ss CM Mi. S I 1 1m0 1 11 CiOn CoM | CSMt 1 CM m |1 sCMt 9 VVOO V. vo vo Hs isH in c m mm mo ms I1 lI -i3n- min 0PO3e -St. vo. CoM st CM CM m CmM VVOO CTi O st m mm st s sc mt min it as o CM min. CM m CaMs n VinO St O st s m cm vo s mat min m ea. in t>0 5 t o P 0 CXQ) <H8 S Tt as c d oa TJ cd o fi CD uX o cas CQ rH as CD CpQ o at SU P ri at sn sa at CQ XI CQ VO 1 p CQ VO 1 (S3 O VO VO 1 9 > VO 1 oo 1> fs> VO vo 11 CQ w M w w w & & && it it -5 s 5 s z x as DUP030012969 I si HH U\ si 8 $ ss .5s e3 S S ao so &a su *Ri6 & RU3 I &8 SI oWo aHo VtO Ot CtnO r- t- t- 4 4ft * i * . w S SH ^ r> ** i it s o S ee * > I ** sa o in in * **4 i ah 8 U St * n .Q w S0 sUI S2&3 *? T fc- VO $ I s4 a o n 4 MS 2 8 88 ( tI i00 <0 9 f%t fSt DUP030012970 FIGURE 1 DUP030012971 FIGURE 2 ELECTRON MICROGRAPHS OP 913-560 CPC HARMON BLUE UNBAKED MILL BASES FILM CROSS SECTION Mill base prepared without vibration.. (Run 40?E-38-(l), Controls 20 Gloss = 25.5) Mill base prepared with vibration and more sand. (Run 407E-38-ab, 20 Gloss = 31.9) DUP030012972 FIGURE 3 -"i: Harmon's blue letdown (901-G-24039) of Flint Dev. Lab. Note the large dark agglomerate. Electronmicrograph of the dry Harmon*s blue pigment Note the darker particle. DUP030012973 FIGURE 4 VIBRATION ASSISTED MILL BASE GRINDING Horizontal -vibration (Earlier runs) DU P030012974 DUP030012975 DUP030012976 FIGURE 7 AIR-DRIED, MILL BASE FILM CROSS SECTION OF 901-550.MONASTRAL BLUE (RIM 579E-I9O). THE DEGREE OF DISPERSION IS BETTER THAN THAT OF FIGURE 2 DUP030012977 FIGURE 8 MILL BASE CROSS SECTION OF $07-686 CHROME YELLOW (RUN 379E-I98). ONLY ONE LARGE PARTICLE SHOWN ABOVE WAS FOUND IN 30 X 5Opt.5 AREA, INDICATING GOOD DISPERSION DUP03001 2978 FIGURE 9' Harmon * s blue mill base ground with -20 + 25 mesh steel shot without vibration (407E-6 Steel) Harmonfs blue mill base ground with PC1-D beta A-B dispersant with vibration (407E-6 V40AB) DUP030012979 DUP030012980 APPEHDIX The following equations relating G, 1, B values of the "Colormaster" differential colorimeter to the a, b, L values were supplied by N. Komodromos of Flint Laboratory. Computer program ML1104 was used by L. Lenhart of Marshall Laboratory to perform the conversion. Lightness - L - 25.29 - 18.58 R1 m 0,8 R + 0.2 B a * 106.0 (R1 ^ - q 1/^) b - 42.54 (G1^ - Bl/3) Aa = asamp_le - a std. AE (Total color difference * (AL2 f+ Aa2 + Ab2)^2 in NBS units) +L DUP030012981 ABSTRACT Vibration assisted "47 Process" sand milling is described. The range of vibration imposed was 13-18 G at 40-60 cps. In particular, a mill base with "Harmon" copper phthalocyanine-blue was investigated in detail. The results showed significant increase in gloss and tinting strength. The effect of denser grinding media also was briefly studied. This study was conduced to obtain preliminary evidence of the beneficial effects of orboresonance assisted pigment milling. With orboresonance^ one can generate 150-480 G at 60-35P cps. The principle of orboresonance'is discussed briefly in the report. DUP030012982 REPORT DISTRIBUTION TO RECEIVE ALL REPORTS ESR REPORTS FULL'. REPORT "FIRST PART11 I mm W. D. Lawson C. W. Theobald P. I. Poindexter R. J. B. C. DRaicvhisards)){ tIn mTurn J. A. Klacsmann W. S. Woods1 C. F. Kalb2 W. H. Edwards i-I. Pappas J. D. Pickens G. E. Lewis C. E. DeBoer S. Hochberg Information Services o /h . Knop V^arshall Lab. Library PRL Library G. I. Mulholland N. G. Fisher (CRD) 1 1 1 1 1 3 1 1 1 TO RECEIVE POROMERIC REPORTS All those listed above plus: R. J. Knake G. I. Jenkins G. T. Vaala B. H. Kirk (Engg.) C. A. Lynch W. W. Bunn, Jr. H. E. Batson E. K. Holden C. E. Correll P. M. Hodgson J. L. Palermo J. S. Allen 1 1 1 1 1 1 1Except Consumer Product reports 2Except Consumer Product and Poromeric reports 1 1 1 1 1 1 1 1 1 16 hh ih i ihh ih 9/18/68 DU P030012983