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MONSANTO TRADE LITERATURE
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C AROCLORS^j"241"
Monsanto Chemicals
As Used in Chlorinated Rubber
Monsanto Technical Bulletin No. P-124
January 1,1948
Monsanto Chemical Company, St. Louis 4, Mo.
AROCLORS, chlorinated biphenyl and chlorinated poly-phenyls, are effective plasti cizers and resins for chlorinated rubber base lacquers, varnishes and paints. These protective coatings are used where flame resistance, corrosion resistance, chemical resistance, i.e., resistance to adds, alkalies and water, and good electrical insulating properties are required. Some of the important applications for these protective and decorative coatings for wood, metal, brick, stone, concrete and fabric surfaces include: 1. Wood and metal used in die construction of yachts, barges and other marine craft. 2. Structural steel for bridges, buildings, roofs and power-line structures. 3. Structural materials used at chemical plants, pulp and-paper mills, textile mills,
petroleum refineries and gas works where protection against add fumes, alkalies and gas is essential. 4. For the protection of tank cars and other rolling stock and construction machinery against corrosive materials and weathering. 5. To protect equipment used in dectroplating and as stop-off lacquers in this industry. 6. Masonry floors and walls. Cqncrete swimming pools and traffic paints. 7. As cable coatings requiring nonflammability, chemical resistance, water resistance and excellent electrical properties. 8. Coatings for doth to impart "waterproofing" qualities as well as chemical and flame resistance.
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Company dUdalmt any liability Incurred In connection with tho uio el that* dote or cvggeorlon*.
Furthermore, nothing contained herein eholl be eomtrued i recommendation to ute any product In conMct with
exlitlng potent* covering any material or Itc uio.
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TOWOLDMON0040027 WATER_PCB-00024496
AROCLORS AS USED IN CHLORINATED RUBBER
' I* INTRODUCTION
Aroclors, chlorinated biphenyl and chlorinated poly-phenyls, are used effectively as resins and plasticizers to impart desired qualities to chlorinated rubber, such as Hercules* Parlon.
Parlon is made by chlorinating natural rubber, yielding a mixture of two polymers possessing an average chlorine content of 67 per cent.
II. PROPERTIES OF CHLORINATED RUBBER
The typical properties of Parlon as given by Hercules Powder Company, Wilmington, Delaware, are listed in the following Table I:
General
TABLE I. TYPICAL PROPERTIES-OF PARLON ?
Form as shipped ; T . . . Color of film.......................... Odor...................................... Clarity of film..................... Taste . . ... , . . . Moisture, per cent as shipped
White granular powder . Water white . None . Good . None . 0.5 maximum
Physical
Specific gravity.................................................................................................. 1.64 Specific volume, as shipped, in cubic indies per pound..........................16.9 Bulking value, gallons per pound . . . / -. y...........................................0.0735 Index of refraction......................................................................................... 1.554
Electrical (dear unplasddzcd film*)
Specific surface resistance, ohms x io10....................................................... 2,000 Dielectric strength, volts per mil (A.S.T.M. method).............................. 2,300 Dielectric constant at 25C. and 1,000 cydes . . . .............................. 3.1 Power factor at 25C. and 1,000 cycles.................................. .....................0.0015 10 0.0030 Power factor at 25C; and x,ooo cydes, after immersion in water for 140 . .. hours and surface wiped dry...............................................................0.0027
Mechanical (clear uriplastidzed film*)
20-cp. type
Tensile strength, pounds per square inch, dry.............................. 4,270
Tensile strength, pounds per square inch, wet.............................. 4,100
Elongation, per cent, dry................................................... r ... 3.6
Elongation, per cent, wet............................................................
3.8
Modulus of elastidty, pounds per square inch.............................. .. 1.4 x to5
Hardness, Sward index, per cent of glass.......................................90
Flexibility of Parlon film increases with viscosity of Parlon used.
1,000-cp.type
4,850 4>36o
3-3 3*4
Thermal (dear unplasddzcd film*)
Burning rate.................................. ..........................................
nonflammahV
Effect ofdry heat on film................................................................ stable up to and at 125*0
Softening point.............................. , ............................................... decomposes at 135 to 150*0
Physical-Chemical (dear unplastidzed film*)
Sunlight, effect of............................................... ....
Discolors and embrittles
Aging, effect of..................................................................................... Very slight
Water, hot, effect of............................................................................. Blushes
Water, cold, effect of.........................................................................None
Moisture absorption (80% relative humidity for 24 hours),
per cent.................................................................................................. 0.27
Moisture vapor permeability of 0.003-inch film (grams water/
square centimeter/0.01 centimeter/hour at 2rO) .... 0.2 x io4
* Films used in tests were kid down from a toluene solution.
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TOWOLDMOn6040028 WATER_PCB-00024497
General resistance to:
Acids, weak , ......................................................................................... excellent
Acids, strong.............................................................................................excellent
Alkalies, weak ..................... v . .......................................................excellent
Alkalies, strong.....................
excellent
Salt spray V.,.......................................................................................good
Alcohols........................................................................................... excellent
Ketones.................................................................................................. soluble
Esters.......................................................................................... ....
soluble
Hydrocarbons, aromatic.....................................................................soluble
Hydrocarbons, aliphatic.....................................................................good
Oils, mineral..........................................................................................good
Oils, animal..........................................................................................poor
Oils, vegetable................. ....................................................................poor
Different viscosity types of Parlon and suggested uses are given in Table II.
TABLE II. PARLON VISCOSITY TYPES
Viscosity'Type
Viscosity Range (in cendpoises) ,. v
5-cp. 10-cp.
20-Cp. 225-Cp. 1,000-cp.
5 to 7 8 to 12
16 to 25 no to 190 800 to 2,000
Examples of actual or suggested applications of the several viscosity types are givens;
Type
Use Examples ~
5-cp. 10-cp.
20-cp. 125-cp. 1,000-cp.
In printing inks and as a fortifier for alkyd resin enamels. In high-solids finishes and as a fortifier for alkyd resin and oleoresinous varnishes and
enamels.
As a film-former in protective coatings and as a fortifier in enamels and varnishes. As a film-former in protective coatings, in paper lacquers, adhesives, and textile finishes. As a film-former in adhesives, textile finishes ana other finishes where flexibility is
important.
III. SUGGESTED SOLVENTS FOR AROCLOR AND CHLORINATED RUBBER COMPOSITIONS
Solvents and solvent mixtures, suggested for use in preparing Aroclor and Parlon formulations are given in the following Table III:
TABLE III. SUGGESTED SOLVENTS FOR AROCLOR AND PARLON COMPOSITIONS
SOLVENTS
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Amsco Solv, B and E Amyl acetate Butyl acetate Carbon tetrachloride Cellosolvc Diacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride Hi-Flash naphtha Methyl acetate Methyl ethyl ketone
Methyl isobutyl ketone Methyl salicylate
Notol Octyl acetate Sovasol Nos. 74, 75 Solvesso 100 Tollac Toluene Union Aromatic Solvent 3553-10 Union Solvent No. 30 Xylene
--4--
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MIXED SOLVENTS
7: 3 97 i 3 8.3 :17 4* : 7 : 35 : >7 30 i 70 18:59:23 64:36 30:30 :40 40:6o
30:70 70:30 85:15
Acetone: hexane Acetone: mineral spirits Benzene: isopentane Cellosolve: ethanol (anhydrous): ethyl acetate : xylene Cellosolve: turpentine Cellosolve : turpentine : mineral spirits Ethyl acetate: isopentane Ethyl acetate: isopropyl acetate: Troluoil Methyl isobutyl ketone: Troluoil Hi-Flash solvent naphtha : turpentine Methyl acetate: isopentane Shell TS-28 : xylene
IV. AROCLOR AND CHLORINATED RUBBER, PLASTICS FILMS
The resinous Aroclors 1262 and 5460 show good miscibility with chlorinated rubber films as laid
down from toluene solution containing 20 per cent of the plastics, using 2 :1 and 1 :1, Parlon : resin,
ratios. Similarly, the plasddzer type Aroclor 1242, 1254 and 1260 show good miscibility in chlori
nated rubber.
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The properties of films derived from the following formulations containing either Parlon and resinous
Aroclors 1262 or 5460, or Parlon and the plasticizer type Aroclors 1242,1254 or 1260 were studied.
RESINOUS TYPE AROCLOR FOR PARLON PLASTICS
Ingredients
Parts by weight
Parlon, so-cp............................................
16 16 12
Aroclor 5460........................................... .... 8 8 8 12
Dibutyl phthalate..................................
4
Tung oil, Thennolyzed, 976 ... .
5
Xylene or butyl acetate..................... .... 76 72 71 76
12 12
3
73
12 12
3-75 72.25
PLASTICIZER TYPE AROCLORS FOR PARLON PLASTICS
Ingredients
Parts by weight
Parlon, 2<>cp...........................................
20 20
Aroclor 1254 or 1260.......................... .... 4
-. 7
20
Xylene . ...............................................
73 70
Examination of the films cast from these lacquers revealed the following characteristics imparted by
the Aroclors:
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Adhesion: -- IJnplastidzed chlorinated rubber films have very poor adhesive qualities. The lacquer film containing Aroclor 5460 gave good adhesion to aluminum, bare steel, primed steel, galvanized iron and Transite surfaces. Other commercially available resins, particularly oil modified alkyd resins, tested in similar films gave better adhesion than Aroclor 5460 to such surfaces as glass, tin, copper, sealed wood and cellophane. The lacquer films plasticized with Aroclors 1254 or 1260 gave good adhesion to Transite, cello phane, galvanized iron and primed steel surfaces. Some of the other commercially available
plasticizers tested in similar films gave better adhesion than the Aroclors to aluminum, tin. Dare steel, copper and sealed wood surfaces. Aroclors, alone, possess pronounced adhesive qualities. Doubtless, where the objective is to produce adhesives, by varying the Aroclor content or by using a mixture of Aroclors in the chlorinated rubber lacquers, much better adhesion to all of the surfaces would be accomplished than was the rase with the type of plastics films studied. Resistance to Aqueous Solutions:-- Aroclors 1254 or 1260 used as plasticizers and Aroclor 5460 used as a resin in chlorinated rubber produced plastics films possessing satisfactory resistance to 10 per cent hydrochloric add, 5 per cent sodium hydroxide, 5 per cent sodium chloride solutions and to water spot tests.
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TOWOLDMON0040030 WATER_PCB-00024499
Film Hardneis Using Aroclor 5460 in ratios of 5:10 and 10:10, Aroclor: Parlon, decidedly softer films were produced than when other commercial resins were similarly used. Likewise, Aroclors 1254 ot 1260 used in ratios of 2 : xo and 5 :10, Aroclor: Parlon, gave softer films than obtained from other commercial plasticizers, used at these concentrations. This indicates the strong plasticizing action of these Aroclors on chlorinated rubber.
Cold-Check Resistance:-- Regarding cold-check resistant qualities imparted to chlorinated rubber films, Aroclor 5460 is somewhat superior to Bakelite type resins, but not as good 8s long-oil modified alkyds. Aroclor 1260 used as a plasticizer rates, in terms of cold-check resist ance, somewhat better than Aroclor 1254 and nearly as good as the best of the other plasticizers studied for this property.
Miscellaneous Properties.'-r- Parlon plastics films containing Aroclors 5460, 1254 or 1260 have entirely satisfactory sanding and polishing characteristics. ^
Weatherability:-- Pigmented chlorinated rubber finishes containing Aroclors have consistently shown good outdoor wcatherability. However, similar unpigmented finishes, regardless of the plasticizer or resin used and also in the absence of these additives, have been found to give poor outdoor weathering. Relatively poor resistance to ultraviolet light is a weakness of chlori nated rubber.
Most pigments, with the exception of ultra-marine blue are usable with Parlon finishes and are reoommended when the ooating is to be subjected to outdoor weathering or exposed to ultra violet light. However, there is considerable variation regarding the protection offered by different pigments: Inspection of Parlon-fordfied alkyd enamels showed the weatherability varied from 63 months for the enamel pigmented with chrome green to 4 months for enamel pigmented with a titanium dioxide-iron blue combination.
V. USES FOR AROCLORS IN CHLORINATED RUBBER COATINGS
A. Finishes for Alkaline Surfaces:
Aroclors, as well as chlorinated rubber, are highly resistant against alkalies and moisture. Because of these properties paints based on Aroclor and chlorinated rubber combinations are used in large quantity for application to concrete floors, walls, swimming pools, etc. Examples of this type of paint are given in. Table IV.
TABLE IV. AROCLOR PLASTICIZER IN CHLORINATED RUBBER PAINTS
FOR ALKALINE SURFACES
Materials
.
(Examples of starting formulas)
Formula 1 for basement floors
Formnln 2 to meet Fed. Spec. TT-P-oi
(Parts by weight)
Parlon, 20-cp. type.......................... Aroclor 1234............................... Rezyl 869 . r................. .... . . . Aroclor 5460 or Cumar Pio .... Beckosofji.......................................
18 10
18 10
6
Tung oil, Thermolyzed, 976 .. . Titanium dioxide.............................. Zinc oxide........................................... Silica flour........................................... Carbon black...................................... Xylene.................................. .... Hi-Flash naphtha..............................
16 2
3 0.2 42.8
16 2
0.5 47.5
Totals..................................
100
100
Formula 3 for swimming pools
14.6 4.4
2.9 4-4 19.7 6'5
47-5 100
B. Acids and Alkali-Resistant Finishes:
Particular care must be exercised in the choice of resins and plasticizers for use in chemical resistant paints. For this purpose, Aroclors are outstanding and are being used successfully in the add and alkali-resistant chlorinated rubber formulations given in Table V.
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TABLE V. AROCLOR PLASTICIZERS AND RESINS FOR CHLORINATED RUBBER, ACID AND ALKALI-RESISTANT FINISHES (Examples for starting formulations)
Materials
z For interior
use against acids and
alkalies
Parlon, 20-cp. t)pe................. . Arodor 5460.............................. . Bakelite XJ-12895..................... Rezyl 807 (solids)..................... Arodor 1254.............................. . 'Arodor 1260.............................. Tung oil, Thermolyred, 976 . Iron oxide.................................. Titanium dioxide...................... Zinc oxide ......... Zylene........................................... Hi-Flash naphtha ....... Toluene............................... .
16 6.4 8
53-6
2 For exterior
use against
acids
For exterior
use against alkalies
4 For maximum resistance to
adds and
alkalies
(Parts by weight)
16 16 18
6.4 6.4 4.8 " 4.S
4.8 4.8 16 16
8 6
18
52 52 39 11
For use against
soap solutions
12 6
7-7
l8 6
28 10.3 12
Totals..........................
IOO 200 too 100
The paints given in Table V were applied to metal bars or panels and tested. Formula i, an interior paint, showed good resistance to a io per cent hydrochloric add solution and to a 5 per cent sodium hydroxide solution. The add resistant paint described under the heading of Formula 2 has shown excellent outdoor protection to metal surfaces on add manufacturing plants. Similarly, paints based on Formula 3 have given good outdoor performance on alkali producing plants. Paint based on Formula 4 was found to have excellent resistance to adds, alkalies and other corrosive materials such as salt solutions. Moreover, this paint showed good adhesion to various surfaces including glass. Paint based on Formula 5 is indicated to have good resistance against warm aqueous solutions containing soap. It should be pointed out that Arodor and chlorinated rubber finishes are not recommended for continuous exposure at temperatures above I40F.
C. Marine Finishes:
Arodor plasticized chlorinated rubber coatings possess good resistance to salt Water and their hard finish deters algae and marine growths from adhering to them. These qualities and good chemical resistance indicates the usefulness of these paints to protect wood and metal used in making boats, barges and other marine equipment. A suggested formula for a marine paint is given in Table VI.
TABLE VI. AROCLOR PLASTICIZER FOR A CHLORINATED RUBBER
MARINE WHITE PAINT
(Starting formulation)
Materials
Parts by weight
Parlon, 20-cp. type...................................................
. 20
Arodor 1254 *................................................... Rezyl 869....................................................................
.6 .6
Titanium dioxide........................................................ Xylene......................................................................... Hi-Flash naphtha........................................................
. 25
. 23 . 20
Total
100
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D. Emulsion Paints;
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Aroclor 1254 is used in chlorinated rubber emulsion paints recommended when chemical resistance is required on porous surfaces. Hercules Powder Company report that the preferred water phases for such paints are either 8 1 per cent solution of Aerosol OT in distilled water or a 4 per cent solu tion of sodium oleate in distilled water. For the complete emulsion* a ratio by weight of lacquer phase to water phase of 2.5 to 1 is suggested. Parlon of any desired viscosity .may be used. A typical paint phase for the Aroclor-Parlon emulsion paint contains the following ingredients:
PAINT PHASE FOR THE EMULSION
Ingredients
Parlon................. Aroclor 1254 . . Cumai Pro . . . Xylene .... Hi-Flash naphtha
Total .
Parts by weight 28 14 10 24
100
E. Adhesives:
Aroclor and chlorinated rubber adhesives are resistant to chemicals and were developed originally for adhering labels to add bottles. These adhesives are also of unusual interest because of their good fire resistant qualities. A typical formulation contains the following ingredients:
AROCLOR PLASTICIZERS FOR CHLORINATED RUBBER ADHESIVES
Ingredients
Parts by weight
Parlon* 125-cp. type............................................................................... Aroclor 1254..........................................................................
20 6
-
Aroclor 1260..........................................................................................
6
Toluene....................................................................................................
68
Total...................................................................................... 100
F. Paper and Textile Coatings:
' - Aroclor and chlorinated rubber coatings are worthy of consideration for spedfic end uses in the
paper and textile coatings fields. In general, however, the use of this type of coating in these fields may be restricted especially where freedom from odor and taste are required. Unpigmented Aroclor and chlorinated rubber finishes would seem suitable for certain fabrics used indoors, but not where they are exposed to high temperatures and direct Eunlight.
O. Coatings for Electrical Apparatus:
Because of their desirable electrical properties, compositions containing Aroclors and chlorinated rubber are very useful to insulate ana protect electrical wire and apparatus from moisture. When fortified with selected fungistats and waxes, coatings of this type are used to "tropicalize'' or protect electronic equipment against both moisture and fungi. Moreover, the fire resistant qualities of these plastics are highly desirable for use in the electrical field.
H. Inks:
Aroclor plasticized chlorinated rubber compositions are very useful for printing inks where faster drying time and increased chemical resistance are desired. The alkali-resistant properties of such plastics suggest their use in the printing of soap wrappers and soap boxes, bottle labels and other commodities where; the ink must be resistant to alkalies.
VI. RESINS AND PLASTICIZERS, OTHER THAN AROCLOR,
MISCIBLE IN CHLORINATED RUBBER
The resins and plasticizers given in the following Table VII are miscible in chlorinated rubber. This was determined by the examination of films laid down from 2 : i.and z : 1, Parlon : resin or plasticizer ratios at 20 per cent concentration in toluene.
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TABLE VII. RESINS AND PLASTICIZERS MISCIBLE IN PARLON
RESINS
Amberol 8oi, 8o(iP, ST-137, F7
Aroclor 1262, 5466
Aroplaz 920, 930, 935, 940
Bakelite XR-3i8o, XR-4503, XR-4006,
BR-2963, XJ-9868, BR-1329, BR-3360
Beckacite 1112
Beckamine P-138, P-254
Super-Beckamine 3501
Beckopol 1400
Beckosol 1 (solid), 18, 31, 34, 40, 1329
Beetle Resin 227-8
Clorafin 70
Copal
Cumar Pio
Dammar
Duraplex C-45-LV, C-48, C-49, C-50-LV, C-5i, C-62, D-61, D-62, E-71, E-71-A, E-73
East India gum
Ester gum
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Ethyl Methacrylate
Esterol 750
Formvar Gelva 2.5
Glyptal 1247,2450,2454,2458, 2464,2466,2500 Lewisol 2L, 28, 33
Methyl Methacrylate Polymers Neville R-3, R-10 Pentalyn A, G, M, X Petrex 1,130H Phenac 633-M Rezyl u6, X315, 412, 775, 803, 807, 829, 869,
880, 1103 Rosin
Santolite MHP Staybelite Ester i, 2,10 Staybelite resin Super-Beckacite 1001 Syatex Hi, H3, H12,17, 213,22, 28, 29, 32, 36 Tcglac 15, Z-152
Velsicol AD6-3 Vinsol
Amylchloro naphtlialene Amyl oleate Amyl stearate Aroclor 1242 Aroclor 1254 Aroclor 1260 Butyl myristate
Butyl stearate Camphor Castor oil, raw
Castor oil, dehydrated Castor oil fatty add esters Cellosolve phthalate Coconut fatty add esters Diamyl naphthalene Diamyl phthalate Dibutyl phthalate Dibutyl sebacate Diethyl phthalate Dimethyl phthalate Fish oil Hercolyn Linseed oil
PLASTICIZERS
Methyl cellosolve oleate Monoamyl naphthalene Naftolen Neville heavy oil No. 2 Nevillite oil Oitidca oil . Palm fatty add esters Perilla oil Polyamyl naphthalene Resinous Products C-24 Santidzer B-16 . Santidzer M-17 Sextol phthalate Sextol stearate Soya bean fatty add esters Soya bean oil Thermoil A Tributyl phosphate Tricresyl phosphate Triethyl citrate Triphenyl phosphate Tung oil, Thermolyzed, 976
The strong points and limitations of the resins and plastidzers given in Table VII relative to the properties they impart to chlorinated rubber are known. None give the important over-all desired qualities attained by the use of Aroclors. If occasion arises to consider the use of these materials in spedfic applications for chlorinated rubber, then more detailed information about them will be given.
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VII. GENERAL Prior to Word War II Aroclors, used in substantial amount with chlorinated rubber, made rapid growth in the applications given in this report. During the war, scarcity of natural rubber curtailed these developments but since the war industry has been quick to resume the use of Arodor plas ticised chlorinated rubber compositions. Their principal field of application is as lacquers, varnishes and paints where flame resistance, cor rosion resistance, chemical resistance, i.e., resistance to acids, alkalies and water, and good electrical insulating properties are required. When properly pigmented these paints or coatings have good wcatherability. Although the adhesion of unplastidzcd chlorinated rubber films to common structural materials is poor, when plasticized with Aroclors strong adhesive bonds are obtained. Aroclors improve the flexibility and life of chlori nated rubber plastics coatings. The formulations of Aroclors and chlorinated rubber along with their suggested uses, as given in this report, are in line with good commercial practice. Much of the data given was obtained from other Anns, particularly Hercules Powder Company, Wilmington, Delaware. The information given is to serve as a guide or starting point in the development of formulations'to expand taking advantage of the outstanding -qualities of Aroclors as resins and plasticizers for chlorinated rubber.
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Monsanto Chemicals
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for farther information about AROCLORS, writ, wire or call the nearest Monsanto office.
MONSANTO CHEMICAL COMPANY
ST. LOUIS
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Reprsrentalhres In Hu Principal CINm of ttrn World
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