a U.S. ARMY FOREIGN SCIENCE ooAND TECHNOLOGY CENTER · certain preparations which have sufficiently...

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I FS'sIrC-H'-2 3-0 34-69 I a U.S. ARMY FOREIGN SCIENCE - ooAND TECHNOLOGY CENTER (0 IRO ZATTACK 6 YMCROGnIS L COUNTRY: USSR TECHNICAL TRANSLATION This document has been approved for public release anid sale- It my bereleased to the Commerce, for sale to the general public. Pop-oduced by thej f-.r Feder.'i Sciontific & TechircalI Information Springfield Vi. 22151J

Transcript of a U.S. ARMY FOREIGN SCIENCE ooAND TECHNOLOGY CENTER · certain preparations which have sufficiently...

Page 1: a U.S. ARMY FOREIGN SCIENCE ooAND TECHNOLOGY CENTER · certain preparations which have sufficiently great practica3 application. At the present time a very great number of classes

I FS'sIrC-H'-2 3-0 34-69 Ia U.S. ARMY FOREIGN SCIENCE -

ooAND TECHNOLOGY CENTER(0

IRO ZATTACK 6 YMCROGnIS

L COUNTRY: USSR

TECHNICAL TRANSLATION

This document has been approvedfor public release anid sale-

It my bereleased to the

Commerce, for sale to thegeneral public.

Pop-oduced by thej

f-.r Feder.'i Sciontific & TechircalIInformation Springfield Vi. 22151J

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DISCLAIIIE NOTICI

THIS DOCUMENT IS BESTQUALITY AVAILABLE. TIH COPYFURNISHED TO1 DTIC CONTAINEDA SIGNIFICANT NUMBER OFPAGES WHICH DO NOTREPRODUCE LEGIBLY.

REPRODUCED FROMBEST AVAILABLE COPY

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TECMZNZCAL TIANSLATION

FSTC-H1-23- 034-69

* CHEMICAL MEANS OF PROTFCTINC NG"ETALLIC MATERIALS

FROM ATTACK BY MI ROORGAVISMS

byN. N. Mel'nikov, I. L. Vladimrirova, S. N. T% ý.ova

SOURCE: KHINICH7Sr;AYA PROMYSHLENNOSTNo. 1, pp. 81-85, 1960USSR

Translated for FSTC by Techtran Corporation

This translation is an unedited rendition of the originalforeign text. Statements or theories advocated or impliedare those of the source and do not reflect the position oropinion of the US Army Foreign Science and Technology Center.This translation is published with a minimum of copy editingand graphics preparation in order to expedite the dissemin-ation of information. Requests for additional copies ofthis document should be addressed to the Defense Document-ation Center, Cameron Station, Alexandria, Virginia, ATTN:

OSR-2.

I

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CHEMICAL MEANS OF PROTECTING NONMETALLIC MATERIALSFROM ATTACK BY MICROORGANISMS

At the present time it is established that practicallyall nonmetallic materials can be attacked to one degree oranother by various microorganisms. The attack of variousmaterials occurs especially rapidly under tropical conditionsat relatively high temperature and air moisture.

Materials of plant and animal origin, and also theproducts of their digestion, are most easily attacked bymicroorganisms. Various synthetic polymeric materials andeven optical glass it 13 also undergo attack by microorganisms.

Unstable materials include: wood, paper and cardboard,nitrooellulos$ , cup ammonium n ayon, biscose rayon1 , poly-vinyl acetate , wool• leather -, refined, unvulcanized, naturalrubberl5, nevea latexi, guayule latex', smoked sheets , Iutta-percha6 , regenerated rubber , neoprene with nutritive additive6 ,Sbutadiene-syrole SK1, Bunr-SI. Buna-H 8 ,12 Isobutylene-1soprene PK , Unvulcanized 0 and vucanized'6 Thi0€l,Phenolo-anilino-formaldehyde resin', alkyd resin

The following materials are stabl I mixed neoprenerubberb,1 2 ,15, silicone resjE, orlon 17, polymethaory.te1 2.phenolq-formaldehyde r sO , urea-formaldehyde resinI ,l 8 ,teflon' 9 , polystyrenel•, ", polyisobutylene 12f20. Accordingto one report neoprene-polyvinylchlorlde is a material whichis resistant to the effect of microorganisms, that accordingto others 8 , 1 0 - it is not resistant.

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In many eases the action of microorganisms does nothave a substantial effect in changing the durability of thematerial, but has a negative effect on its externalappearance, and also on its electrical propertles1,1 4 .Thus, the specific volume electrical resistivity of certaininsulating materials (polyvinylchloride, plasticized resinand perohlorvinyl coatings of various resins, lacquer coatingsand many other materials) drop 100-fold under the influenceof molds.

It should be noted that the resistance of plastics tomocroorganisms has still not been studied adequately inrecent times and there is much data indicating the vulnera-bility of various materials which were previously consideredto be completely resistant. It has been established positivelythat all articles from very different polymers which containcellulose as filler and other organic substances capable ofserving as nutritive media for molds and other microorganismsare very vulnerable to microorganisms 1 .

The prevention of growth of microorganisms on variousarticles can be accomplished by many methods, of which thefollowing have practical importance: application of materialsresistant to the action of microorganisms, and addition ofspecial antiseptics which kill microorganisms or inhibit theirgrowth to materials.

It is necessary, however, to indicate that materialswhich possess absolute resistance have still not been foundat the present time and frequently growth of molds is observed

.on relatively resistant materials which have no nutritivemedium at all for fungi, and are conpaminated by organic sub-stances from the atmosphere and soill.

Due to the most extensive distribution mentionedabove, protection of various materials from attack by micro-organisMs was obtained by means of addition of special anti-septics to them.

The most extensive use of antiseptios was attained forprotection of wood- material which is used in extremelydifferent fields of industry and construction. Withouttouching on questions of proteotion of wood, which were con-sidered in print several years ago 1, that the rate ofmanufacture of antiseptics for wood has continually enlarged.This Is quite convincingly clear in the case of Pentaohlor-phenol, whose use for antiseptic treatment of wood in the2UsAincreased from 126.7 tons in 1945 to 5,138.1 tons in 195822

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We note that antiseptics which are effective for onetype of microorganism may appear to have little effectagainst others. The materials into which the antisepticsare introduced, and also the conditions of introduction ofthe antiseptics and the treatment of the material appear tohave a great influence on the effectiveness of the antiseptios. I

There are indications in the literature that dven the solvent 9may have an effect on the activity of the antiseptic 3 , which 4

is especially important when using antiseptic for paint andvarnish coatings. The pH of the mediu also has a substantialeffect on the activity of antiseptiosq.

Usually the following general requirements apply to

antiseptics: the presence of fungicidal end bactericidaleffect against a wide circle of microorganisms, chemical and Iphysical stability, absence of odor and color, low volatilityand low solubility in water, etc. Moreover, an antisepticintroduced into a given material, should not effect itschemical and physical properties, should not harm the qualityof the article, or change the technology of its preparationand harm the working condition. Antiseptics should be suf-ficiently inexpensive and have comparatively low toxicity foriiumans and animals. Antiseptics which simultaneously satisfyall the enumerated requirements have not yet been found,although more than 3,000 compounds have been published in theliterature, which have been tested at various times in verydifferent materials. Practical application has been obtainedfor an extremely limited number ol substances.

In a short review it is not possible to give even asimple list of the antiseptics which have been studied up tothe present time, and we are attempting to mention onlycertain preparations which have sufficiently great practica3application. At the present time a very great number ofclasses of organic compounds have been studied as antisepticsfor various nonmetallic materials, including phenols, nitro-compounds, halogen derivatives Of hydrocarbons, simple andcomplex ethers, salts of various organic acids, heterocycliccompounds, quinones, amides of Acids, organic compounds ofmercury and tin and many others 2 5a.

Of the phenols, the most widely used as antiseptics fornonmetallic materials are the tri-tetra- and penttc4oghenols,which are used for protecting paper and cardboard,-'cotton and other fibers of plant origin2Z9 -3 5•.plastlc sub-stancesl.5 *3 ?, paint and varnish coverings36, 3'43, leather44,45,

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certain other materials from attack by microorganisms.Usually these phenols are introduced in quantities from0.4 to 2% of the weight of the dry material being preserved.In several cases in order to increase resistance in thepresence of moisture antiseptics are introduced along withhydrophobic additives (most frequently bitumen, paraffin orsynthetic resins).

Of the subs t ancef R•t•ge phenol type 2 2"-dWoxY-5.5'-diehlordipheeIy tan± -o, -nltrophenoli,49950,oxydiphenyl- , 5 ,, 0-naphtnol 9, have also received some

application as to antiseptics. Thus, n-nitrophenol provedto be a good antiseptic for leather and natural and syntheticrubbers.

It is appropriate to note that as a result of prolongedaction of sunlight almost all halogenophenols impregnatingplant fibers, break down with the formation of hydrogenchloride, wrqch results in some reduction of the durabilityof the fiber.

Along with free phenols, their salts with various metalsare als$ used: copper, zinc, silver, cadmium, etc. Interestingresults were obtained, in particular, with silver pentachlor-phenolate, which was used for protection of cotton fabric inFlorida (USA) over a period of two years in air and for morethan three weeks in soil. After remaining for two years inopen air the fabric treated with 1% silver pentachlorphenolate,lost only 11-13% of its original durability, while controlsamples had centergraded by 90-100%. Somewhat poorer resultswere obtained by treatment of fabric with copper pentachlor-phenolate. Inasmuoh as under the same conditions after twoyears the durability of the fabric was reduced by 25%, andfabric treated with free pentachlorphenol, had deterioratedby 77-95%.

Mixtures of various phenolsI, and also mixtures ofphenols wlth ketones and halogen derivatives of aromatic hydro-carbonsl1 '9 possess increased activity. 4,9'- dinitrodiphenyl-carbonate 6 0 has also been proposed as active antiseptic forleather.

Copper 8-oxyqvMIolate which is used Zor protectionof textile products 2, 56, 61-e9 including fire hoses, cottonand parachute tabrios and various other materials used in

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airlplane oonstruot~on23,56, lacquers and paints 7 0 - 7 2 . andplastic substances57.73, have received wide applicationfor antiseptic treatment. The addition of copper 8-oxyquin-clate, and also other copper compounds to natural rubberleads to rapid aging, while oertain synthetic rubbers inthis case proved to be resistant 5 7.

Copper 8-oxyquinolate is added in a quantity from 0.5-8-10% depending on the material. It may be added by variousmethods, for example, precipitation of the material as aresult of reaction with inorganic copper compounds with saltsof 8-oxyquinulate. Or in the form of solutions in variousurganlc solventabY or in the form of its aqueous suspension.and also an emulsion of its solutions . The presence of acolor is a substantial drawback of this antiseptio (as it iswith almost all other organic copper compounds). which to acertain extent limits the possibility of its use.

.Recently, the use of 8-oxyquinolates of cadmium7 4 ,lead75 , and other metals as antiseptics for various materialshas been patented.

The use of copper naphthe9nte, use production in theUSA in 1958 exceeded 1,000 tons7 has reached significantlevels. Since copper naphthenate has an unpleasant odor andstains mfterials, it is used mainly for treatment of cruderarticlesl. Along with copper naphthenate, the use ofnaphthenates of other metals and their mixtures with coppernaphthenate has been proposedI. There are data in the patentliterature on the high activity of copper salts of variousother organic acids as wjll (for example, furanoarbonate andfurandithiomariDamaete?.?, and also steario, palmitio, andolelo acidsA).

Dinitrofluorobenzene, dinitroflurobromobenzene, 1-fluor-o-3-chlNo-0# .6-dinitrobenzene and l,3-difluoro-4,6-dinitro-benzene ,3 are interesting antiseptics for various aviationmaterials and especially plastics. These compounds are quitesoluble in organic solvents and in many high polymers, arecolorless and have practically no odor. They signiflantlysurpass phenols and oxyquinolates in microblologioal activIty.Fluoron14ro•enzene is also suggested for use in protectingleather24,57. One must note, however, that it is rathercomplicated to obtain these compounds (with the exception of2,4-dinitrofluorobenzene), as a result of which their cost ishigher than halogenophenols and 8-oxyquinolate derivatives.

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Several other halogenonitrobenzenes have proved to be Potive Ifungicides for the protection of leather79.

Organic compounds of tin, which are close to organiccompounds of mercury in the strength of their effect arenew, promising antiseptics fo-z, nonmetallic materials 66,80-86.The minimpl concentrations of several organic compounds oftin, which completely inhibit. the growth of fungi requiredfor characteristic fungicidal activity of this group ofsubstances are presented in the tableO2,9 3 ,9 2p.

Fungicidal Activity of Several Tin CompoundsMinimum concentration for full stoppage

of rowthBotrytis- Penicillium Aspergillis RhizopusCompounds allii ita] I icul niger nigri cans

Trimethyltinacetate :. 2,Trie thyltinaoe tateTripropyltinacetate.Trilsopropyltinacetate ,Tributyltinacetate 1.Trihexyltinacetate .Trioetyltinaoetate , ITriphenyltinacetate I =DiethkylphenyltInacetate e 1

Diethyl-n-Bromophenyl-tinacetate :

Diethylbutyltinacetate ,Die thyl hexyltinace tateDie thyloc tyltinacetate

Phenylmercuriaoetate

Organic t~ compoungg are good antiseptics for wogd 82 ,83 ,cotto aind Jute , paints , paint and lacquer coatings,paperol and other materials. Organic tin compounds bgan tobe used as agents for protecting plants from diseases #9'and for preventing slime formation in the paper industry8 6 , 8 8 ,as effective substitutes for organic mercury compounds, lesstoxic for humans and domestic animals 95 .

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In industry the acetate ani oxide of tributyltin hashad the widest aplAl1catio n , and in agriculture - triphenyltin-acetate.

It is interesting to note that several organic compoundsof tin are stabilizers for various plastic materials, increasetheir thermal stability, prevent ~ellowing and increase theduration of service in sunlight. 8 ( YU. The stabilization ofpolyvinylehloride resin by organic tin compounds is ofpartioular interest.

Organic compounds of mercuryI,20O3 6 , 6 6 ,9 6 -103, whichare recom ''e1e8 f2 treatment of textile materials', w•oodand paper P,1ZOO , Y,0 plastic msterialsl, 2 O,9 , resin 9 9,lacquers and paintslOO± ,I, are used as universal antisepticsfor many types of nonmetallic materials.

These compounds include phenylmerouriaoetate, -phthalate.-su.lfamide. -oleate, pyridylmercurlohloride, alkylmerouiroleate,ethylmercuriphosphate and several others. Usually organiccompounds of mercury are used in quantities from 0.1 to 1%of the weight of the treated material, considering dry matter".The general disadvantage of these compounds of mercury istheir high toxicity for persons and animals, which is aggre-vated by their ability to accumulate in the organism and tocause serious chronic poisoning. The high toxicity of organiomercury compounds for humans leads to the necessity oftaking speolal precautionary measures both in their produc-tion and in their use, which significantly increases thecost of production.

A negative property of organic mercury oompou-nde icalso their low stability in relation to soil microorganisms,by which they are broken down according to the followingschemes 2BHgX + 2H R 2 Hg + Hg + 2HX

Inorganic mercury compounds 1 0 2 have also been proposedas antiseptic for nonmetallic materials, but their effect Issignifioantly weakez as a result of which they must beintroduced into the treated material at higher quantitiesthan organic compounds.

Salicylanilide is an Intersting univergal antisepticwith low toxiolty for humans, which is recommende4 for pro-teotion of paper;1 . texti 4 mn!erialsel p.astics 0,106,lacquer and paint coatings ,IO5 resins and other materialsI.

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Salioylanilide is pooily soluble in water, rather stableto heating and comparatively inexpensive. However, in orderto obtain a good protective effect, salloylanilide must beIntroduced into the treated material at high quantities(3-8%) which in many oases shows up negatively in thepropertios of the treated material. An especially pronouncednegative effect of salloylaniDIde appears in lacquer ooatingsin which the preparation sometimes separates in the form ofcrystals.

There is some use of quaternary ammonium saltsl07-IIIwhich possess comparatively weak fungicidal activity, butmore bactericidal. In view of its good solubility in waterIts applioation is expedient only in oases when the treatedmaterial is not subjeoted to systematic effect of water.

Along with the substances mentioned above as arli 5 ptiosfor nonmta1lio materials, 211-jiohloronaphthoquinone *

rh danjne.ll.2 salicylaldox mel, certain pyridine derivit!.ves114,ii.D zinc thlodyDteI1 n-toluolsulfamidelj• d g ....various other acidsIl and many other oompounds-,01 OA39are also suggested.

The use of antiseptios for protection from mioroorganimshas great signlfioanoe not only for protection of variousnonmetallio materials, but also for other purposes in certainfields of industry. Protection from biologlotl growth isespeoially important in the paper industry. According todata of various investigators boiological overgrowth ofapparatus in paper factories in thi ULM results in annuallosses ef about 25 million dollars . Organic mercury ....- 122compounds, their mixtures with phenols aU iyquinollne 1 ,and also the hydrate of tributyltinoxide O*OO, have beenused recently &a agents for combating biological overgrowthin the paper industry.

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31 (1954); C. A., 52, 20843 (1958).31. 8. D-h±, A. Kaplan, J. Am. Leather Chemists Assoc., '2,

536 (1957);C. A., 12206 (1958).32. USA patent 2649451, 1953.33. USA patent 2688627, 1954.34. USA patent 2637661, 1953.35. USA patent 2376650, 1945.

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36. H. Rabste, Ind. et tray. Outremer, 6. No. 53, 207 (1958).37. French patent 1129636 RZhkhim, No. 11, p. 495, 1959.38. J. Leopard, H. Pitman, Ind., Eng. Chem., 43, 2328 (1951).39. A. Williams, Ind. Finishing 6,434 (1954).40. G. Genin, Lalt. 32, 218 (1952).41. USA patent 2153841, 1938.42. Japanese patent 4937 (51).43. USA patent 2153842 (1938).44. A. ue J. Turner, J. Soo. Leather Trad., 35, 290

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16, 013 (1957).64. R. Rose, M. Mitton, Appl. Mioroblol., 3, No. 2 (1955).65. R. Rose, C. Bayley, Am. Dyestuff Reporter 44. 648, 676 (1955).66. S. Freysohuss, Norsk Skoging, 12, No. 3 104 (1958).67. C. Bayley, Appi. Miorobiol., 4, No. 2 (1956).68. R. Rose, C. Bayley, Textile Research J., 27, No. 7 (1957).69. Patent of the Federated Republic of Germany 935515;

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74. Patent of the Federated Republilo of Germany 936607C.A.., 53, p. 4643 (1959).

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103, (1958).80. English patent 7431191 C. A. Vol. 50, 12156 (1956).81. P. Heron, J. Sproule, Worlds Paper Trade Review, 148, 1815,

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110. English patent 703477, 1954.111. Swiss patent 292326, 1953112. C. Brown, Ind. ng-. Chem., 46, 1508 (1958).113. USA patent 2822297. 1958.114. USA patent 2658850, 1953.115. Canadian patent 501851, 1954.116. Federated Republic of Germany patent 9326321 C.A., Vol. 52,

p. 20863 (1958).117. Federated Republio of Germany patent 942718; C. A. Vol. 56,

p. 4642 (1959).118. English patent 788943; RZhkhia. No. 14, p. 555 (1959).119. S. Swohse, Dtsoh. Farben Z., 12, 233 (1958).120. J. Stg, J. Freysohues, Svensk. Papperstldn., 59. 223 (1956).121. J. Freysohuss, Svensh. Pajpperstidn, 58, 815 (1955).122. J. Person, T. Petterson, Svensk. Papperstidn., 57# 801 (1954).

-12-

,I

Page 17: a U.S. ARMY FOREIGN SCIENCE ooAND TECHNOLOGY CENTER · certain preparations which have sufficiently great practica3 application. At the present time a very great number of classes

UNCLASSIFIEDfteurttv Cleameiicatioi 0:"3

DOCUMENT CONTROL DATA - R &,V,; ....(Secu•ityr cIoitkst4ioNf of Iltis, body . h c a nd Indexing Annotation ... be .nf.-rd vh*n the ovell report is c€lauflsedt

I, ORIGINATING ACTIVITY CSp•.to Authorj 2. REPORT SECURITY CLAIISIFICATION

Foreign Science and Technology Center UNCLASSIFIEDUS Army Materiel Command 2b. GROUP

Department of the AramyI. REPORT TITLE

Chemical Means of Protecting Nonmetallic Materials from Attack byM icr oorgani sms

4. oocnipTivIa NOTKE (re "o of owt amd incluijve dotes)

• TranslationS. AUTHOR4(0 (PIdtI 1WW, mi.4IN Int'F8-, Mea0t nem*)

N.N. Mel'nikov, I. L. Vladimirova, S. N. Ivanova

S. REPORT DATE 17a. TOTAL NO, OF PAGES NO. OF IRES

8 May 69 12] N/AGo. CONTRACT OR 4RANT NO. .. ORIGINATOR'I REPORT NUWVCERIS

b. PROJIKCT NO.

FSTC-IHT-23- 034-69

9223628 2301 lb. OTHER REPORT N0o4S (Aily othertNmbSeIs 1a o.asl14pe'

4 P. Cushing ACS1 Control Number (None)10. iOISTRIDUTION STATEMENT

This document has been annroved for public release and sale; its distributionig _unlimited.

II. SUPPI.-EMENTARY NOTEIS 12. SPONSORiNG MILITARY ACTIVITY

I'S Araiy Foreign Science and Technology

Center

11. AGSTRAdT

Various antiseptics are suggested for protection of susceptiblematerials of plant and animal origin as well as certain syntheticpolymers from attack by microorganisms. Antiseptics shouldpossess fungioidal and bactericidal properties against a widerange of microorganisms, chemical and physical stability, freedomfrom odor and color, low volatility and low solubility in water,and should not effect the chemical or physical properties of thetreated material or the quality of the article. In additionthey should be inexpensive and have low toxicity for humans.Antiseptics discussed Include: phenols, 8-oxyquinoline derivitivesnaphthenates, nitro- and halogen derivitives of benzene, organicand inorganic mercury and tin compounds, and quaternary ammoniumsalts.

,, .-- ;., eRU •14r. UN L AS WHICN Is

DI Nov~sv GoDVII% i a UNCLASSIFIEDECurity chesifleadon

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IKOLK MIT ROL MI OLK WT

antlacpt2.osfungloidesbaciterioidesnonmetallio materialsmiciroorgani.am.

UJNCLASSIFIEDsecurity Clegoiflceti~e