CA2101947A1 - Fire extinguishing and protection agent - Google Patents
Fire extinguishing and protection agentInfo
- Publication number
- CA2101947A1 CA2101947A1 CA002101947A CA2101947A CA2101947A1 CA 2101947 A1 CA2101947 A1 CA 2101947A1 CA 002101947 A CA002101947 A CA 002101947A CA 2101947 A CA2101947 A CA 2101947A CA 2101947 A1 CA2101947 A1 CA 2101947A1
- Authority
- CA
- Canada
- Prior art keywords
- fire extinguishing
- preparation
- thickened
- water
- fire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/266—Esters or carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3227—Ethers thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Emergency Management (AREA)
- Business, Economics & Management (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Fire-Extinguishing Compositions (AREA)
- Fireproofing Substances (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Production and use of thickened sludges of synthetic amorphous silicic acid or bentonite in water as a fire extinguishing and protection agent in which the water is mixed with preferably 1 to 7 % wt. synthetic amorphous silicic acid and the resultant thin fluid suspension is rapidly thickened by the addition of a small proportion of polyethylene glycols of molar mass of 700 or more or of polyoxyethylene fatty alcohol ethers, fatty acid esters, polyoxyethylene sucrose alcohol fatty acid esters or polyethylene imine, or said substances are premixed and then intensively mixed with water do that the aforementioned percentage weights are attained, or the aforementioned minor additives are dissolved in water in suitable quantities and the silicic acid is added in solid form. The use of this thickened water preparation can, for instance be used as a fire extinguishing agent in ordinary extinguishers or in the form of fire protection cushions, for instance, to prevent fire propagation.
Production and use of thickened sludges of synthetic amorphous silicic acid or bentonite in water as a fire extinguishing and protection agent in which the water is mixed with preferably 1 to 7 % wt. synthetic amorphous silicic acid and the resultant thin fluid suspension is rapidly thickened by the addition of a small proportion of polyethylene glycols of molar mass of 700 or more or of polyoxyethylene fatty alcohol ethers, fatty acid esters, polyoxyethylene sucrose alcohol fatty acid esters or polyethylene imine, or said substances are premixed and then intensively mixed with water do that the aforementioned percentage weights are attained, or the aforementioned minor additives are dissolved in water in suitable quantities and the silicic acid is added in solid form. The use of this thickened water preparation can, for instance be used as a fire extinguishing agent in ordinary extinguishers or in the form of fire protection cushions, for instance, to prevent fire propagation.
Description
` PCT/DE92/00070 2101~3~l7 E~e e~ n~S~ protecriol~L a~ent ~; an e~ti3lgu~h;i~g agent wate~ e adYa3:L~g~s of hi~ heat absorbi~Lg capaci~y a:nd there~ore favourable cool~g ac~ion7 ~ ~c o~ to ic~ compa~ibility with ma~ i3~able materials, ine~en~i-veness a~d ~ ally a ~sood a~r~;l~ility. It is ~erefore sti~l an i~oxtant i~re e~ingui~ g age~t.
A known disad~ e o;E water a~ an ~tin~ishi~ ageIIc is its ~.~ly liq~lid ~ature, so that d~i31g the esti~ishi~g proce~s lar~e quant itieS flow a~ sed and i~L p~ ca~e ~ece~ ~ter damage~
l~re~ore only a sm211 part of ~he sp~a~ed wa~er has it~ fa~ourable e:ctingui~hi~ ac~io~ co~si~r-;n~ of cooli~ t~he ~i~g mate~ial.
Tnere~ore ~ero~s attempe~ have been mate to im~rove water as .
fire e ~ inguish ~ g ~ge~t.
Th~s, or e~a~le, the addi~ion of i~bstan~es hav~ been tes~ribed~
which b~ing iabo~t i rise in lt5 viscoisit~, such ias cellulose deri~a~
~i~e~ z~natei3 or w~ter-soluble sy~thei~ic polymer~ ~Gh ~s pol7 acr~ de~ ~se îs lso made o~ ~io~ sDmable mnneral addi~ives to ~e estl~g~ishi~g water, e~g. w~t~r-soluble i~organic saltsi or water-in~olt1ble ~terlals such as bentoDitei or a~i pul~i~e (cf~
nllm~n~s ~nzyklopadiei der TechDische~ Chemie, 4th editio~, ~ol.
11, p~569 i~nd ~l ~ s E~c~clopedl~ o~ I~d~strial Che~istrY~ 5th ~di~io~, Vcl. A ll, pp. 114/5).
~`
I~ ~pecial ca~e~, sach as whea fightiDg ore~t ~iles, ~se is e~.
made o~ be~tonit~, a~tayilYi~e ~nd water-soluble sal~ ell as e~t~ng~ishlng w~t~r ~o~lat~o~ ed wi~ ~ ates ~nd which af~er special preparat~on are frequentl~ ~jected ~rom aircrat ~cf.
e.g. ~.E. Hardy, Chem~cals ~or Forest Fire Fi8ht~n~7 3rd edition, ~os~o~ . ~e to nmnerous disad~ aged such e~ shin~s a~e~ts ha~e only pro~ed sion;f~ca~t ~or fight~ 8 orest fires a~d c~m~u~ be ~sed for g6~eral p~rposes.
:$j~L~
A known disad~ e o;E water a~ an ~tin~ishi~ ageIIc is its ~.~ly liq~lid ~ature, so that d~i31g the esti~ishi~g proce~s lar~e quant itieS flow a~ sed and i~L p~ ca~e ~ece~ ~ter damage~
l~re~ore only a sm211 part of ~he sp~a~ed wa~er has it~ fa~ourable e:ctingui~hi~ ac~io~ co~si~r-;n~ of cooli~ t~he ~i~g mate~ial.
Tnere~ore ~ero~s attempe~ have been mate to im~rove water as .
fire e ~ inguish ~ g ~ge~t.
Th~s, or e~a~le, the addi~ion of i~bstan~es hav~ been tes~ribed~
which b~ing iabo~t i rise in lt5 viscoisit~, such ias cellulose deri~a~
~i~e~ z~natei3 or w~ter-soluble sy~thei~ic polymer~ ~Gh ~s pol7 acr~ de~ ~se îs lso made o~ ~io~ sDmable mnneral addi~ives to ~e estl~g~ishi~g water, e~g. w~t~r-soluble i~organic saltsi or water-in~olt1ble ~terlals such as bentoDitei or a~i pul~i~e (cf~
nllm~n~s ~nzyklopadiei der TechDische~ Chemie, 4th editio~, ~ol.
11, p~569 i~nd ~l ~ s E~c~clopedl~ o~ I~d~strial Che~istrY~ 5th ~di~io~, Vcl. A ll, pp. 114/5).
~`
I~ ~pecial ca~e~, sach as whea fightiDg ore~t ~iles, ~se is e~.
made o~ be~tonit~, a~tayilYi~e ~nd water-soluble sal~ ell as e~t~ng~ishlng w~t~r ~o~lat~o~ ed wi~ ~ ates ~nd which af~er special preparat~on are frequentl~ ~jected ~rom aircrat ~cf.
e.g. ~.E. Hardy, Chem~cals ~or Forest Fire Fi8ht~n~7 3rd edition, ~os~o~ . ~e to nmnerous disad~ aged such e~ shin~s a~e~ts ha~e only pro~ed sion;f~ca~t ~or fight~ 8 orest fires a~d c~m~u~ be ~sed for g6~eral p~rposes.
:$j~L~
2~19~7 l~e re~so~ e e.g. ~e gener~llY necesSary hi~h Jeight pe~centages of n~Lneral additive~; in order to ~cbieve a sllfficien ly ~gh le~el of thicken~ng (e.g. 10 to 20% by wei~ht), the corrosive action of certai~ sa:Lts such as sulphate~ or chlorides, or the pos~ibility of ~md~sired en~ironmental i~fluences occur~i~g, e.g. of ~ertili2illg compo~ents, whose qua~ity application on que~:g a ~ore9t f~e c~n e~g. be a ~ le ~ rface area of the ~ ilize~ ap~l~ atio~L
in agrlcult~re. The prepara~on of ~ch thicke3~e~ special e~
s~i~g ~g~nts generally regn;res special appara~ d par~ læly this a~pl~es wit}l res~ect ~co ~he ni~g t~:Lereo~. ~Che~ ~ general not be ~pplied ~ing convention~l fire e~nis~;ng sy~inges ~nd e.g. ~ ~e case of algina~e g~ms do not ~aYe 23~ op~imum ~d}lexing ~ction ~o ~e suri~aces follo~i~g s~pray~ng, ~articr~ y ~de~ thé
action of heat, ~he~ freque~tly c~e their use cha~acte~stios sfter eveIL a shor~ ~torage period a~d, a~l:er d~il~g, sometimes leave beh.r.d d ~ ficulty removable resid~e~3. .
The prepa~ation of a thicke~ed e~tin~uishin~ water ~ithou~ these disadva~ta~es, p æ ti~ularly a non-1ammable thickening age~ for the water in order ~o ;mprove the wa~er e~ti~uishi~ ac~ion9 is ~herefore highly des~rable. A~art rom ~he posit~e e~ects o~
adhesion to soIfaces, e~en i~ the case of e~e~ated temperatures, the formatio~ o co~esive 8~tin~ulsh~ ag~t ilws with 2 partic ly high wa~r percen~a~e a~d ~fie~entl~ high stability~ ehem~
ical and phy~iolo~cal ~ompa~ibllity with all dead a~d living mR~er-~al3 oecurring d~liLn~ th~ extin$uishing proces3, t m~3t mai~taîn its Use properti9~ eve~ fter prolon8ed storaQe a~d, if ne~es~ry, .
m~ be~;p~e~a~bI~ iQ a rapid, ~^~espen~i~e manner.. b~.m~ ng with .. ... !-'~
ordilu~r~ wat~r nd ~nst be appl_able ~si~g conventionally a~ailable flre e2tinæ~^shi~g ~qu~pment~ At ~re~ent the~e îs no ef~icie t fire e~tin~ui~h~3g age~t7 which s~îs~ies all these requ~^rements.
Ce~;n o the requisite cha~ac~eristics such as a broa~ compatibil îty w~h li~ d dead material are ~.g. f~lfil~ed ~ omo~pho~
. .. -. -. . - . . - . . . - -A~
2 1 0 ~ 7 .
~l;ca or s;1icic a~ , so that the l~tter i~; no^c onl~ widely us~d as a thicke~ ag~t ~cf. U~ln~ns ETlzyklo~adie d~ Tech~ische;~
Ch~e, 4th edit~oIl, Vol. æ, p. 473; 1~ k ~ e~ c~rclopedia of Chemical Te~hnology, Vol~ 20, p.778j E. Brunner, D. Schut~e, Chemiker Ztg. 89, 1~5~ pp. 437-40; H~ Fratzscher, Farbe u~a Lack, 75, l~69, pp. 531-53~). It ha~; a pa~ic~la~ly mar~ced t~bicke~
action ~n the form of ~med 3ilica ~re~ed by flame hydrolysis in non-polar 1ia~id~. In polar l~quid~ such ~s water the ~hickeD~ng ætio~ of said silic~ is less prouo~c~d, so that it ;q ~ecessary to ~dd relatively large q~n~ities for obtai~ing a si~nific~t ~hick-~ning action. It is aS ye ~Ot kno~n ~o use 3;Iicas in ~he ~orm of an a~eous s~s~e~ion fire e~t~guîshin~ a~en~s. Fumed silica tæ o~ly described a:3 a pulre~en~ speclal e5~t;ng~isn;ng ~ t for ~ ~ial ~ire s~Ltllations ~EIIB 0339 162 Al ox }~I}B 03~ll 006 ~l). A~
a ~esult o~ its e~:~reme ~ ness7 its general ~se as ~n esti~ui-shing age t iæ not p~sc~cabls.
I e.g. ~umed c;l~ca is sus~ended in water, mnch ~ore ~an.10% is ~eeessary in oraer to obr?~n a usable th~ckeni~æ ~nd th;s suspension also beha~es i~ a ~ otropi~ ~anner. This is a ~is2dv~ntage for u~e with standard fi~e ~tinguishi~ ~qui~ent. ~ e.g. a 5~ su~pel-slon o fumed sil~ca ~ wat~r ls spr3~ed ~rom di~ferent ~praying means, li~uids ~ass1n~ thinly out of th~ nozzles are alw~s obtained ~nd th~y ~u~ o~ surface5 i~ the same way æ wate~ a~ti~8u~shi~g comparison tests o~ gtand~aiz~d ~ises, su~ un~hickesea ~iLica S~BpellSlOng ha~e no better aCtio~ than water, . ~ , .
It ~s alsoAk~own~`th~t suspension~ o ~mor~houa~s~h~G~c.,sil~cas i~ wate~ oves a period o~ tlme (~e~erall~ w~eks or ~o~hs) sl~ly have ~ te~de~c~ ~o the a~lo~esation of particles 2nd to settli~g phenoDie~ owe~e~, this n~c~en;r~g effect~ is ullimportan~ fos the prese~ set proble~ as z resnlt o~ its slowne~s and limited e~ent. Ihis process, altho~h it can be accelerated so~e~hat adding electroly~e~, d~es ~o~ sepresent a sol~tion o~ t~e ~re~en~
proble~. S~k suspe~sio~ ~hickened by l~a~ing ~o sta~d also bec~e ` ` 21i ~1~4~
hi3hly l;q,~id a~2:~L ag ~L res~lt of 9tir~i~g follow~g p~olo~ged storage, i.e. whe~ aying us~ng conventional fil~ e2ti~guisher s~r~Lges said tl~o~ropic liq1lef~c~ion ~ aisadvan,,ageous, beca2lse ea~ly i~rpair~ ~he adhesion of the water e~i~}ce~ed i~ way.
~s shown, an e.g. ~ suspeD~3ion o~ umed silic~ water, followi~g thick~ as a res~lt of ~to~age, beeome~ highly ~ id ag:~;n on sprayi~
The ~roblem there:Eore arise~; of ~rov dis~ impro~ed fi:re e~ting~
uish~Dg agent of ~he ty~e o~ a thicke~ed extinguishi~g wster, par~i-c~larl~ ~a~i~æ an only l~mi~ed ~el~ht perce~tage o.~ s~nthetic amorph-ous 5ilica or oe~er, ~on-1~mable, broadl~ compatible minerals ~n the ~o~m o~ a 5u~pension in w~r s4 as to ob~n a th~ckenin~, whi~h takes place ~nsta~taneo~lY and ~ a ~o~rollæble ma~ner, gives ~ ~ea~y defined a~d s~able fin~l state and ~s not so thi~o-trop~ed by the spraying process th~ its adhes~o~ ~c~io~ p~i-red. It must also be ~sabl~ with oonve~tio~a1 ~ir~ e~ guishe~s and it5 pre~aration must not require 9pe~i21 eq~ipm~n~, whils~ havi~
a g~od adhe~ive action to bo~h ~r~.~.l and dowawa~dl~ directed smrEaces, espedall~ at elevated temper3tures. I~ particular, its e~tin~ h~ng action must be far superior to that ~f water.
~ccordin~ to the in~en~io~ this problem is solved in rh~t a th;ck-ened su~penYlon of amorphou~ gynthetic silica ~n ~ater is prep~red by misin~ erulent, ~umed sllica with wa~er and 2 compo~nd o~
the tgpe o~ a ~olyethyl~e glycol with a molar mas3 of ~700 to c600,00n7 deriYati~es o pol~e~h~le~e glycol ~uch 3s e~hers wl~h fatt~ alco~ol~ stér~ h fatt~ acids, ether~ w~th ~ar~ohydra-tes of molar masses 300 or blgher, ~s well as ~;th polyethylene ;mine, l~e necessary sil~ca concentration~ in wat r are ~ery low.
The~ only represent a ~r~etion of the amounts ot~erw~se re~uir~d f~ ~h~cke~ng ~n aq~@ous s~qpensio~, nsmely 1 to 7w compared with . .
~10%~
`` -~ 2~ a~
~e said additi~e~3 ca~ be added to t~e h~ id su~ ion of Si~iCZL ~ water, to the actu~ ates, bu~ can also be dr~ prPmi~ed with ~e siliea. In ~11 cases ~ eo~sly ~sable, ~ickened e~ ;ng w2ter 1~ obtained, which ca~ be ~ her tbickened i~ co~trol:Led m:lnn~r~ e.~. ~y the shear~g actio~ present ~ a fi:~e e::tingui~hi3~ pUIlly~ o~t ~y ~pai~ g o.~ the spra~ing ~ acit~.
On t~e ~:on~:r~, as a reslllt of the flow ~ ac~e~istics obtai~ed o tl~e th~s tbi~kened e;~ ~sh~ng wate~, co~p~red ~rith co~ntional water7 it~3 s3~ra~i~v cha3~acteristics a~e ~mpro~ed, e.g. wit~ respec~
to l~he range or lo~er :Erietional los~es.
The la:;t process caIL be referred ~o as rheope~ A.~ the additio~
~hiclce~ng ob~i~ed he~e ~ no~ los~ ag~i~ when che ~ea~i~ action is stopped, refereslce co~ld be ~ade ~o a~ ~irre~ersi~le rheo~e~y".
A~ a result ~e ~3e ~ tlle presently descri~ed ~icls~ned s~spension of ~morpholl~;, ~ Lthetic silica as . fi~e e~ti~g~shing agellt is p OE tic~larly sY ecti~e, beca~se 1~ a ~ery shorr ~e with a normal e~nO~u~sher 12sOe sa~aces can be thickly co~ered with the ~ighl~
ef~icient e~tinguishing ag~nt, no matter ~rom wha~ m~terial they are made or whicl ~eometrical ~o~it~on they ~e. ~de~ ~he action of heat ~he~e 1~ no decom~o~itlo~ of 3aid coatin~, such as a sofee-ning or ~l~pping o~ ~p to the drying of the wa~er.
The wz~er thickened i~ ~he ~bo~e manner bas a n~mbar of essenti.l advantages~ s~ch as ease of 3pr~yi~ or spr ~ g by means of ~a~i-0~5 type~ of fire ~tin~oiahing ~mps or ~yTinges in accorda~e with DIN (b~cket s ~ e/TS 2tS), a~ well as b~ me3ns o a hig~ ~
pres~re pump ~ing 'a working pressule of 100 bar, ~p~l~cability ~rom ~nd f re es~i~gnisher~, ~dhe~ion o ~ven thick e~tinguishi~g a~e~t layer~ of se~eral ce~tim~tres up to the evaporatio~ or drying o~ ~erti~al a~d doN~wardly directed surfaces h~ng differe~t Ghara-ct~ristics a~a mzde fro~ di~e~ent ~ater~alsO ~$ the ead of the Lire ~iO~hting me~sures the esti~gui9hing s~ent can be e~s~lg ~emoved in dama~e-ree ma~Yr ~om the s~b~erates ~n questio~J e~8. b~
` ~@1~7 s~raying off with water or by suction ~i~g conrentional ~nduclt~ial sllction eq~ipment. As ~e t~ickened e~i~ ish~,~,g ~ter i.s uot los~ thro~gh ~n~ away, it c~ be taken up a~n ~ollowi~g t~e e~tin~ishinæ process, s~ ~t co~ation of the ~ iro~ment by produ~ o~ ~ehe f~xe ~lowi~ awa~ with che e2~in~ishi~ water aIld also ~ater d~mage to b~ildi~s can be l;~n;ted. ~er dryi~g the ~i1;ca ge~ left b~ d b ~ ~d~orbi~g ch~racteristics, whlc~
~a~ also be ~ræ~tageo~s ~or ~kn'ng up decompositi~n products of the fire or other con~ auts.
It i~ par~l~ul~ d~a~tageo~ to ~tilize t~hi.s ~oper~ of ~he fir~ e~ iS~iP~ ~ge~t according to the ln~e~on by sucki~g in the dry pre~ix o~ the amorphous sili&a with the thickener i~ ~
e~$ing~d~;n~ water flow, ~e desired t~icke~m g taking place ins~an-tsneously. It is noteworthy that an addition o~ sli~htly more t~n 1~ o~ e.g. ~med silica to th~ ws~el is adequate f~r ~his p~rpose.
For cert~in applic~t~ons i~ ~zn ~l~o be advantageous ~o ~se large~ -3ilic~ q~ ties ~n ~ater, e.~. in orde~ to form with the e~tingui-shi~ agent a b3rrier ag~;nst the u~controlled flowing out of l;q~ids ~o~ the ~e areQ or the ~cki~g up ~ction o~ ~he sili~a for a~
cont ~ n~s present~ ~bo~e 7% silica i~ the ~ater w~n usi~g con~e-ntional e~ing~i3h~rs no lo~er a~plicabl~ pastes form, but these ~a~ be ~sed ~s ~ire protection masse~, beoau~e the~r ~om4geneit~
i~ ret ~ned even w~en there ~s a high water content and a low silica co~tent. A silica ~el obta~ned f~om water ~lass b~ neutraliz~ug and washi~g or by ion e~ch~nge and given a pas~y cetting is o~ly homogeneons for a ~hor~ eim8 after ~r~paratiOn a~d then q~ie~
staxts to gi~e of~ water i~ e~nsiderable ~uantities. Tbe ~ire prote~
ct~on mass prep~red 2ceordi~ to ~he inYention avcid~ ~his ~heno~e~on in the case o ~ h;~ w~t~r and low solid percent ge. These flre ~rotection masses are s~i~able ~n nmmerous wayæ fcr preve~t2tive fir~ protection for flammable str~c~res, in fi~e-retarding barrier ele~ehts or ca~la lines3 p~l~iColarl~ thos~ w~ich are seDsiti~-- 72~~9~
to corroslo~, fire decom2ositio~ produc~s or o~tflswin~ water.
me "thickeni~g aaa~ es~ used æcord~38 to t~e i~vention are ~qui-red in ~11 cases i~ only extremel~ ~mall weight co~ce~trations.
~ith the pref~rabl~ ~sed progortio~s of only 0~003 to 0.2%, ~ased on the total qu~ntity, they 3le soarcely ~oticed. Seqeral o~ the thick~ng addi~i~es described are con~ent~onalt~ ~lsed 35 emmlsi-~iera, eOg. f~r ~reases, wa~es or as spe~al sur~a.:tants. The "~loc-cnla~io~ o~ silica b~ polyglycol is co~sidered usef~l e.g~ for ~ater puri~ io~. It c~Dnot be co~cl~ded ~ro~ P~t;ng teachi~gs ~h~t a suspensio~ of ~ a or bentonite of abo~e 1% i~ water ~aQ
~uaaenl~ be made ~o uniforml~ ~hi~ke~ ~hrou~h the ~dicated compaunds of ~olye~gle~e gl~col~ o~ h~d~o~y~thy1~ted fat~y a d d, ~att~ alcohol o~ sug~r derî~ati~e~ or pol~e~hyle~e i~i~e, i~ ~e case of the sDall-e~ weight percentage~ ~hereoC and ~hat the th~ckeni~g actio~ obtai-- -~ed c~n be maint?;ned ~or a ~lmo~ unlimlted tim~, so that the eh~s obtained e2tingnishi~g agents ca~ be s~ored or ~s~d i~ s~atian-ar~ e~ti~gu~shi~g e~ip~e~t~ o~ tha~t the she~r actions occurr~
a~rin$ e~inguishin~ do no~ act i~ ~he form of a thi~ot~opizl~g and insee~d prod~ce a type of "irre~ersible rheope~izingn, which greatly ~a~ours the use as a~ hing ~ge~t by produc~ng sta-ble, adhering Wat~r layers. Thi~ i~ surprislng beca~se the aore-me~tioned compo~d~ OEe not o~ the co~ention~l th~ckener ~pe.
It is also indicati~e or the present inve~tio~ the described thickaning no lo~e:r OCClIr~ a~ co~eeIItratio~ls o~ ~he ~ i.c~cen~ng addiJGLve~ of the polge~er ~ype ~bo~e c~ lim~r.s t ~ t .5~) or t~L~ ~e addi~ion of concen~rstions a~ t~ickeni~2; additires of the polye~ier t~l7e abov~ these v~1nes to already ~c~cened ~pensioLs brings abo#t ~ r i~nmediate ~d ~e~ent dil~tion o~ thinnin~r 0We~6~, thi9 iS not a problem in ~ractice, be~ 3~ addition be easily n-~ored.
A~ incre~sed plI-~alue has a simi:Lar action o~ ~he efIec~ of ~h~
pol~ether type ~clcF~n~n~ age~rc. ~$ pE~alues abore 8.6 ~here iæ
-8 2~Q19~7 a reliq~efaccio~ of already t~ickerled suspensio~s, -~ich ~ ~1so ot ~sad~ eous, because ~or the e ~g handliIu, oi~ the e;cti~
uis4i3~ ageslt the pH~val~e is chose~ as close as possible to the netltr~l point. C~30ne~ts æ~i~g i~ a hi~ly ~1k~1ine ma~ner can conse~erltly not be added ~o ~e ~hickened ect~ g a~e3l~ form-cio:Qs whe~ ~s~g polyosyeth~le3~ derivati~es.
Tr~ the case o~ ether~ hieke ~ g ~dditi~res a~L e~ception is fonmed ~y compo~Dds h~ViD~ a weak alk~line ~ction suc~ a3 bi~arbo~-ate~. They are compati~le wi~h the ~hicken~d s~2ensio~s of amor-phous, sg~thetic ~ilica n a~y 501ibl9 co~c~ntration. For e ~ le, potassi~m h~dro~e~ carbon~te can be ~dded up to i's saturat~on conce-~tration o~ appro~ately 34%. Duri~g e~ icarbon-stes can decompose, accompa~ied b~ ~he rele~se o~ c~rbo~ dio- de, which incre~ses ~he e ti~iS~iD$ actio~. The suspensioD~ of a~or-phou~, sy~the~ic ~q~l;ca thicke~ed accord~g to the ~nve~tion ~re also compat~ble ~ith other, not stroDg alkaline sal-~s, e~g. ~rep2r-atio~ oan w~t~o~t di~icilty take place wit~ sea ~a~er, or pota~sium solphate, ammon_um phosgha~e or boric acid ca~ be d~sol~ed i~ the th~ckened s~S~Pncion~
Wkereas the thicke~ing addi~i~e polyethylene ;m;~e br~g~ sbou~
a stable ~hick~l~n~ action in the squeo~s silica susp~nsion i~
alkaline range~, the~e i~ a reliq~efac~ion in the strong a d d range~
In a~ ca~e, acid conditio~ are a~oided to pre~ent cvrrosio~.
~ow~er, if necessary, a com~ination o~ ~h~ two ~hi~keniDg addit-ives is po~s~ble a~d then, as desired, ~h~ck~ning can take place ~ ed~ther ~he acid o~ ~e a~cali~e ra~ge~
~ .
T~e described t~ic~ening e~fect is partic~ ly mer~ed With f~med silica. ~s is shown in the e~amples, i~ the case Oc precipitation silicas the nece3sarg co~ce~r æio~s for obt2iDin~ æ clear rhick~
2re m~h higher (5 to 15~) and the aah~sic~ actio~ ~s less satisf æ -tory. ~we~er, precipitætion silicas are less e~pensi~e ~hsn fmmRd ,, , . _ ............................ .. .. .
,.~`.',. - . ' ' ' ':
' ..................... . ' ~ -`.-.: :' -- . , 2~01 ~
_ 9 _ silic~:.
e~pensire b2se could be p~o~ided b~ silica 501Q e~g. ~repared by ne~raliza~on from wa~er glass, ir it was po~sible to pre~are therefrom w~tho~t grea~ time and ~roc~ss e~pendit~re a homogeneo~sl~
~hlck~ed s~spenslon. Although s~lica sols, if the~ ~e not ~abili-zed, ha~e a tende~cy to ~elllng~ i.e. to the form~tion of a cohesiye gelatino~s mas~, the latter ;~ ~ns~ltable ~or ~he presen~ ~et ~rob-lem, becan~e t~ere iæ a poor ~dhesiPn: to surfaceq a~d o~er a period of ti~9 it ~eleases the w~er contained ~here~ and grad7~ally also h~sdens, T~elr ~ ticles ~e ~o~ ~e~erally displaceable agal~st o~e ~other a~ t~e ti~e of ~o~stio~, i.e~ ~o flow ~haracterl~ic3 e~ist. By d~persi3$ s~ch sil~c~ ~D~l~tinou_ ma~Ds it is ~lso p~sgi ble eo prep~re thi~ke~ed, aq7teo~s ~lica ~nspensions partl~ suitable for ~ire e~tl~g~isbi~g purpose~ is ~lso possibl@ to lea~e the relati~ely lo~ salt co~tent present i~ the ~ase of 2 ~sa~le thi~ke~-ing in a~cordance wi~h ~he ne~trali a~ion process 2~d this does not impair the e~tinguish~n~ ac~io~. rhe thic~e~d su~pensi~ns o sy~thetic, amorpho~s silica prep~red by means ~ neutrali~a~on processe~ do ~o~ behave ~u rheopectic manner i~ the same way as ~hoqe prapared _rom ~umed ~ilica~ Ihey are suita~le in ~h~se sit-natio~s, where the ra~d ~ncompli~ated preparation ~n situ or direct ~reparatio~ i~ the fire ~tinguish;ng process is not as decis~ve as the ~ g o_ ~ire e~tiDgui~e~s or statio~ar~ e~t ~ ishi~
equl~ment.~.
I~ solviog t~e s¢t ~roblem o pro~iding ao ~f'ect~re and w~dely co~patible ~ire e~tin~9~iDg agent ba~ed on a th~ckened ertingu sh~g w3~er i~ has been!~o~nd that~ a similar ~n~er ~o the sylthe~
~lc, amorpho~s cillca, b~ntoni~e, sta~ting from a hi~hly lig~id s~spension iQ w~t~ with ODl~ a limited eoncentrz~io~ can be rapidly ~d d~rably ~:o3l~er~ o ~pr~y2ble, adJ~ re, t~icke~ed 5usper~i-OD~3. This e~fect wh:~ch immediatel~r occ~rs with rgorous ~ir~g ~s not as pronounced as ~i~ :Eumed si~ he ~chicke~
2 1 O ~ 9 ~ I
. ~ -- 10 --additi~e~ de~ribed i~ the inve~tion the ben~oDite whi~h in low co~centrat~ons only produces ~h;n s~spensions can be con~erted in concentrat~o~ of l.~X in water into thicke~ed su~penslons in water nsa~le as fire e~tingaighing ~ge~ts and has a good 2dhes~vo action to sux~æ es. ~owever9 ~he s2me e~ect ca~ot be a~hieved with ~he k~ow& thicken~rs such 2~ gu~s, pol~a~rylamlde a~d the like wi~h mol~- ~asses of ~6ao,000, or g~la~i~, at least i~ the prese~tly described lo~ ben~o~ite conce~tx~tions~
~ithin the 5cope of the inre~tlon the stabi ~ ~ion of the deqcri~ed fire e~ti~shi~g a~en~s agai~9t frost a~tion by the additio~ o~
cQmpound~ of the glycol or gl~ce~ol t~pe ~s algo fo~nd ~o be advan-tageo~s~ Co~po~nds e~ecti~e ~or ~rost and oorrosio~ prote~tio~
l~ke borates, c~n, if nece~sarg, be ~sed. It has been ~o~d ~ha~
a sig~ificant atdition of these compo~nds ~o p~o~ect against frost does not ~m~ir the ~hicheDi~ ~ctio~ or 3tabil~t~ o~ ~he thicke~ed fire ~tLnguishi~g agents described.
~he ~oUowin~ esanples ~ strate the inyention ~ thout res~ricting . .
the same.
~mple 1 (general preparation e~ample) ~-10~ o~ ~omed oillca ~¢sco~l 200, re~i~tesed tr~d~s~k ~L D~uYsa, Gesm2ny) were suspended 1~ 190 to 196 ml a water, accompanied by s~i~ri~. The re~ultlng suspens~o~s sre hig~ly l;qu~d wlth p~ e~
o ~bout 5. If the~ ~re not stron~y s~rred, the~r ou~loN ~l~es in ~he DIN c~p ~4 mm ~ozzle~ OE~ ~ to 11 seeonds, ~t ca~ be ~p !.,,~'`,`.,:~'':::,.'~:.' .. '1 ~0 14 se~oads.~f:sli~ht ~gglomer~ion occurs. I~ ~t~rring takes . ~ o~
~l~ce with aQ elect~ical Btirring ~od ~appro~imat~ly 800 ~.p~m~), the~ become e~ more hi~hlr t;qn^d with a~ out~lcw time o~ 9 ~ecn-nds, ~om~arabte ~ith ~he ris~osi~Y of water. To ca~d s~s~ensions are xdded a ~ew drop~ o~ polyo~et~ylene la~ryl e~her of mwl æ mass 3ppro~m~ 380~ or a 50g aqueo~s solution of poly2~h~1e~e ~lycol 210~9~7 of mD~ ~ 4220, or ~ S0,~ aaueous solution OL polyo:~yet~Lylene so~itan mo~os~rate o~E molær ~ss 2~pro~Da~ly 12G0, or a conce~-t~a~ed solu.ion o~ ~120 jojo~z aoia and PFG-i~) "o~ob~ ~lcoho7 e cose;ly; or dot:ose~yl ac~d~ l~ohol ro~ ~o~obz oil i;~. ~tho~-,~lated fo~), or a ~ ?olyeth~le~e imin ~o7~ion (~ol~r~ ~, registOEed e~rad~-r~c o ~sASi~ I~.~osh~ e~, &er~zn~? ~"d mi~n3 ~lace b~ ~ rrirl~ ~ith 2 s~tu~a. .Ir. R11 C~3es ~ere i9 2~.
tely~ elearl~ no~ice~ble thickening to ~ ho~geneo~s~ ~iscous ~usp~:io;i w~. as3 ~ f~ctf.on o~ the si.7,~ por~ion, ~s preel7-qd ~o ~ ~raryi~g e~ent. ~lo~ t~ of 14 - ~ 35 ~ec~nd~
o~cu~, or past~ ~s~encies a~e pro2uc2~ wh~ not be deter7 ~ned ~n the o~"flow cu~, but ha~e a ~ood ~r2,,~rlg or adhesion c2~-ae~ , OrL accnrate ~ hin~ o t~e necessar~ um, au~ ities Of ~he ~dicated 2~aiti~e~;, it i~ fo1md t~at e~en 0.007~ ~35 ppm~
æe e~f~i~e, a~d ~.a~ in the ~se o~ ~olyo~e~th~lere com~o~nds ~ere is a~ m;,, ~ ap~ro~imabelv 1.5% in ~he o~e.~l., ~re, above ~ch r~ e~don oc~srs. If th.e l~.h~s o~t2i~ed, lo~g ter~
~-~able, t~ickened sll~persio3~ of s~lic2 undergo z~ eren brief~
rous stirr~g ~e.~ ~t~ an elee~ ,irrin~ rod?, t~e ~icken~g sig~i~icantl~ i~c_ eases Pnd re~ins ; n ~-; s 'or;~ t is e~sil~
~o~sib~e ~o spr2:~ these l~boraeor~ c u~n~ 2 s~ e bo-..le ~.ith or wi~out ~n at~zin~ no~zle. On ~ t all ~urf2ces, such as wood i3~ ~rea~ad or ~ ~shed form, plzstie, rubo~r, 8h8s ~.
metal tm~oblemati~l ~dhesiorl 1~ pa~s~ble~, e~e~ reater layer knesses~ out anv d~sadvanta~eous ~hange ta~ pl~c~ to tbe layer ~ ru~ng out. slidi~ o~ or w~ch ~n 2!1~ other wa~
~mp ~Ir~ the ~ire e:~tin~ actlo~ s ~n ~aF~icular ~plie~
to hot 3urf~ces, w~e~e ~ere ~ no sl~ding o~, ~e s~ ed or -~p~inkled surf'aces dr~ w~thin 12 to 48- hourrs; ~s ~ fu~ction of the - -layer ~ick~esses a3~d ambien~ con~iti~rls. The dr~, usu~ l~k~
like sil~a le.'~ b~.~d can eesil~ be me~h~n~c2ll~ re~o~ed ~om the s~2ces z~d c~a e~f~ be seadily b~shed ou~ ~ro~ .abric~.
21 ~9~7 ~a~Dl~ 2 (Ge3lerzl pre~aratiOn e~ample) 4--lOg o~ ~umed silicz ~re ~ed ~th i:~ ea~L c~se 0.3~ of polyo~
ethylene lauryl ether o:r polyeth~ene glycol of ~l~r mas~3 ~0 o~ polyetl:~ylene glg~col sorbita~ mono9te~;3,te (molar 1~1aS9 appro~-;m~tely 1200~ or PEG-120 ~ojoba acid a~d Pli~-l~O jojo~z ~lcohol9 or polyethylene ~ne, so l~at ~ d~ prem~ oL~ed. For this pt~rpose po~$ tal~; plae~ o~o 200 ~1 o: wate~, followed by m~
w:Lth arL electric 1 9~g rod (bl~de diameter 3~5 cm~ appros.
80~3 r.p.m.), so th~t pzst~r consisl:encies are obta:ned. 0~ addillg 150 ml oi~ water ~i~C0~:3 mspe~ons axe ob~ed ~ o~l ow ~i~cosity o~ ~4--30 seco~Lds i:n t~le D13!1 ~up (4 mm ~lozzle). The ~ara~
c~ tics of t~e res~lting l;hi~ d sil~ spensio~s, w~
are also di~ectl~ ob~i~ed by add~ the elrti~e 3SO ~1 ~o w~ter, relre 1 310 dife~e~ces compared with t~he su~pensio~Ls ~bta:~ed i~
comparable concentra~ioDg i~ ple 1..
100~ o:E a dr~ ~re~ of i~umed s~l~ca ~9?g) a~d ~olyo~yethylene la~l ether (3~) obtai~ea accordin~ to l~bis e~le are fillea ;nto a stor~ge ~ sel and, u~g a s~ction hose7 whic~ pipe connec-tion has ~ ~eed i~Lto a ~ ~ater 10w~ is s~lcked by meuls o~
a ~ ht vacuum ~nto s~id wate~ 10w, followed by m:L~i~g ~nd thic~
enia~, so tb~t ~ wator p~ss~g ollt o~ ~ ~lightly narrowed glas~ :
no2le only ~ ew cent~met:res a~ter the ~i~g point ~lrezldy has a~ escell~ dhesio~ to a g~ss su~ace. Fnr ~cJ~ng in the dry prend~;, it is al~o po~3sible to ~se the ~et~on side of a water jet pump ~nd the sur.king ~n of ~e ~lverlllent pre~ can be continned o~ a long time ~i~chout p:coblems or.blo~ es. 33g a corresporLd~
sion~g of ~he ~u~eiol~ eeds, reg~lating the ~ter ~alltity and ehe water pre~sure7 ~che ~;c~e~ ~roced~re can be eoll~rolled ~L t~e desired man~ ble thiclceni ng accordi~g to this proce~
dure is e.g. o~ ed ~ith a silica co~eent:~atiOn of oDly 1.3~ i~
water.
_ . , . _ . .. .. ...
21019~7 :e~3mple 3 ~ ddi~ gela~cin solution (which ha~ dy bee~ describad as predpitant for s~.lica sol, b~t ~ a we~ht ratio of ~lmost 1:1 ~y l'h~, Gr~h~m, Philos. Tra~Ls, I~don, 186~, pp. 2~5/6) a l~ keni~g of the ~med silica suspe~sion similar ~o 13;c2mple~ d 2 is obt~i-ned with low concentra~ions of e.g. 0~1~ ga1~ , b~t su~ suspens-ions reveal m:Lc~obi~l co~ ion a~ter a ~ela~-Yel~ ~;hor~ ~iod.
~! t~0mPaXi80n e~ample) T~e t~c:kened silica slls3~e~dons obts:~ned accordi}Lg to l~am~les 1 a~d 2 were miæed with in each case ~ sodillm ~bonate aIld bora~, so t}at pE-Y~l~es of 11 or 9.1 ~e obta~ed, ~ere~3 ~Le ~iclce.~g disappeared im~ed~Ltel~ ~er aaditio~ with 211 ~e pol70~yet~hylene de~ivati~e~, it rem~i~ed in 1:he case o~ a polyethylene iD~e thidcen-ed si~ca suspe~
E~le 5 (~omparisop, e~;ample) The ~bicke~ed silica sllspensio~s obt~;ned accord~$ to }~ample~
1 and 2 were nr~ced with ~n each case smaLl ~mo~Lts of hgdrochlo~ie acid ~ Lt~ a pE3: o~ 1 was ob~ ed, and ~i~h i~ esch ca~e ~% ci~e scid o~ a~cor'oic ~id ~ntil ~e~ g a p~ of ~ a~d 3. I~ the case o a~l pol~o~ethylene co~po~ds the thicke~ing waY ~ta;ned ~n these add ranges~ Eoweres, when mi~ed with poly~ yle~e imi~e ~ r~liq~e~ ion was obs~rved.
........ ~
le 6 (Prepara~ion and lls~ with a b~cke~ s~ 3e) ~6g of f~med siliaL were sti~red with 11.68 litre3 of w~ter. I~fter lea~ ng to st2~Ld for one hoar with occ2sional sl;~ ;ng, a viscosity o 13 seconds was mP~ ured i~ a DIN ou~flow cup. 35g o~ polyo~y-ethyle~e la~l eehe~ we~e added, acwmp~ed by ~ g, ~co ~is " 2~al~47 hioj9ly iir~d sus~enslo~. ~ e- e S~:or~ t e ~e ~scosit~ o the E~eure rose ~o a p2S'C~5 ..ez~''y s~irrable an~ uo~S~e cous~s;e~}c~.
10 lle~es of ~he ~hlls ~-c~en~ e3ri;~ishinc w~;~r-~ere .i~led into e ~c~c~t sy~ee a^~o~d~ to nI~' 14L.r~5. T~.o resul~ ic'~
er.ed esL;~ g ~d~er p~o~ed ~o ~e sp~a~able ri~h ~ ~ltipurpose ~e~ pipe 1~ ~c~ord:Lr.g to DIN 1~.~3S5, ~ D~inY t:he s~
process there was a cle~, fu~Lher ~hicXeni~g o~ ~e ~teri~1 p~S9i~
ou~ o~ ~ 3~t p~'pe a~ colDpare~ ~iLtn ~ Oduc~d ;-~o ~he btl~k2 syr~nae, ~e s~ra~ea maLe.i~ a ^~ersr goo' adhesio; to a ~OE~i-cal, ~ai~ed co t:rete ~r~ce ~ d~ng ~n?ll)~ er spra~il~ ap~
~ma~el~ S l;~res~ ~:he re~ in~ ci7e li~r~s lef~ !be~ d 1;~ ~e buc~et s~ e ~ere ~ ed with h~e same aol~n, Of ~ e by a~,~t~arL
~r~d ~he s~ra~n~ proce~s was ~ontin~ed. ~en with th~s redu~ion o~ the conce~stratio~ o~ the thicke~ed silica sus?e~sio~, a ~ood t~ll adhesion on s-or~ stil~ cc~urred~ her s~ in~ ~e~ts good ~dhesio-~ ~a~ ~o~d ~o ~rdboard, ~iood aDd ~ ftter lea~
ir.~ to st2nd f~r 14 m~nt~s, t.~ s~ a~oidi g eq~poration losses, no ~ettl~ng o~ -~e ~teri31 tH~S detecte~ z~d ~t co~-la ~ill be r~ad~t ~l~ spr~yed.
e 7 ~repa;zLion ard use t~h 8 P3~LCb1 WOE 31i~) 10 '~8 of fume~ si:L~ca wer~ st~rred i~to lS~ .res o~ water. Th~
r~g~ultln~ sus~ens~on coh~aine~ easily crus~le p~ c~es wi~h a ~a~eter of ~- ~o ~ ~, w}lich slowl~ sedimented on the ~o~.tom on lea~g to s~and. T~e sUpe~at~nt sus~ ion no longer l~ad ~y ~articlss and had ~Lhe c~a~acteris~Li~s o~ a clol,;~ silioa sol, uh~ch st~ on~a~ed 3 s~ ter lea~i~g. to :star& . ' or- 6 ~eecs t~alri-- . .. -: .~. --metric de~er~atio~ af~e~ dryi2g and 'æ~). The ri3co~ty of the sed~e~ted sil.ica sol w~s a secon~s in ~Lhe I;3:h' ou~ow cu~ a~t2r 6 t,Teelcs stor ge, but 11 s~conas ~i~ec-l~ fQlk~ ?reæ~a~io~, i,e, ~r-t1~ ~e ~ti~ s~s~ended ~ar~-cle~. S ~les c~ ~.~ sol cl~i-fieâ or p~ied ste~ s~t-1:~8 and thos2 q'C~ end.~d .
..
~la~7 matter w~re co~vertable wlth the additives ~eferred to i~ E3ample 1 and i~ the co~ce~trations give~ therel to a th~ckened silica s~speDsion. The still unthickened suspension wa~ stirred wit~ a padd~e mn~er a~d the res~ltis$ 200 litres were sepa~ated into two ide~tir~l pærts. ~he part was stored ln se31ed ~orm w~tho~t f~r~her addi~i~e~ far obserYin~ the lo~g term beba~iour. Over a twal~e month period rh~re was a slo~ ~hickening and ~ettli~g o~ ~he hottom oa lea~ing to stand o~ said ~ ca s~p~sion ~ot p~o~ided wi~h the iDdicated addi~ives. Eowever, it was still miable ~nd spray sble tbro~æh ~o Y-le~ a~d b~came highl~ liq~id ~aiQ by thi~otr~p-i2i~g. It co~ld be thickened by the additi~es r~erred to i~ ~a~ple 1 a~d conv~r~ed into a thicke~ed, aq~e4~ 9ilic~ ~c~speDsio~ bl~
as a~ adhe ~ fire e~ti=~cish;~g age~t. The oth~r par~ o~ the mis~re w~s mixed wi~h 250g of polyo~ye~hylene lauryl ether immediat~
ely ~ollo~in~ prepara~ion a~d stirred with a paddle ~dser, which led wlthin appro~ately 30 seco~ds to the ~ni~or~ icke~i~g of the eIItire s;~ usp~sio~.
The ~h~.~ thicke~ed eYtiDg~ishin~ water wa~ sprayed in proble~-free ma~ner as both a ~11 iet an~ as a spray jet ~siQg ~ portable po~er pump TS 2~5 accord~ng to DI~ 14410 with a mnltipurpose ~e~ pipe C accordin~ to DI~ 143~, part 1~ ~s In E~ample 7, there was a d ~ar further ~ckeni~ of ~he e2tinguishing w~ter by the pumping and 9~ra~iD~ proce~s~ Good ranges ~nd an e~cellent wall ~dhe~lon to ~ertical s~rfaces we~e obtz~d. ~s l~ Example 7, i ~ece~ry, further ~hlnni~g With watflr wa~ pos~ble Nhi1st maint~1nlnv the c ~ acteri~tics.
Ate~ se,:.the t4ickened, s~raged e~ting~ishi~g:::wate~ ~o~ld be taken~p ag~ln b~ shovelll~g or sactio~, so that ~ ir~ re3~lti~g p~od~-cts contal~ed therein only passed t~ a limi~ed e~t-~t, if at ~11, nto the so~l.
The eg~in~uishi~ ~ater ~rom ~his ~i~t~re ~hioken~l ~y ~d~;ng 2101!~17 -- lo --polyo~yle3le lauryl e:ster, like the silica suspP~sio~ withou~
the additive, w~s let to sWd for 12 mont~s. ~ re wa~ b~
tially no chan~;e ~o its llse be~our aIId ~o se~di~8 of residues c~ ~e bot~osll of the vessel. Withoul: preservative sl~reS, there were ~o cle~ar b2cteri~1 conta~i~R~cion phe~Lo~e~a ænd it mU5~ be ~o;n-ted out tha~ ~ sa~le used iIl an e~guis~ g test, which was COllt-nnn~ted b~ a cert~i~L amo~nt o:~ soil had, on the basis o~ its s bee~ conta~ated 8:Eter a ~ [owe~sr, ~o s~e~l pre~3er~
tio~ me~es ~re reqtl~red ~ he c~3e oi~ cle~ stora~se~
~e e~t~ishin~ test) 1~ tes~ re wi~h solid ~}elg o:~ fire Class A ~woo~ien cri~, 40~40 cm, 7 l~ye~s, ~reb~g ~e 4 m;n.) was e~lin~s~ed ~ith a ~pra~
iet ~ 7n~c7~ened e~ ;hi~g water, prepared æcordi~g to E~as;r ple 7 ~nd set to 2.5 aD~I 3% SîO2 coneeP.t. Co7~ ed with the ex~-g~.s7hi~4s te:~ ~th ~ater, fo~ ~guishi:n~ p7;~o~es oD3~y lJ4 of ~he e~ting~i~hin$ a~e~t ~ua~tity was con~ned ~d the Ilumbe~ o~ ~ ~
rei~tions decre~sed to l/4. ~thP ~dher:~ layer of thi~ened e~
gUi6h:1143 ~ates del~yed or preve~n~ed f~re ~ropaga~orL and i~ition of those p~ o:E the flammable ~erlal ~ot affec~ed by t~ fire.
The l~r~e allso~ of 5~eam fo~med reYeals t~ he r~;ckeled ~
ap~lied is al~ot3t ent~ely a~aîlable ~or eool~g and e~gt~ g R~cse~, beca7~se it doe~s ~ot ru~ o:E~ the b7~able 7~rts and ~nto ~h8 8ro7~d. l~e 8~3ent î~3 suitable fo~ es~7~g~ing f~am~able ma~er-ials s~ch ~ woad, pla~3tic7 ~bber, wooden m~ter~als, t~stile-s ~qnd othes orgaIIict :solid mBtf~i.al5.
(Fi~e OEt~i~ test) ~~ `: -`
13-A fi~e ~ccording to RFS ~423) was e~ci~;~ed ~ h an e~ctls~g-g wate:r form~latio~ pre~ared with ~ ~% thic~e~Led qil.ica su~pen-s~o~ accordi3lg ta F.~ample 7. e e~ gni.qh;ng a~en~ ~eo3~ io~
~ to co~plete es~ was only 1.? kg. O~ly 50~ of s~.l;ca ~, ... : . :: , .. ;. " ~ , .. . . .
2 ~ 7 ~e~e co~ med for comple~e e~g~ishing o the fire. The qua~tity o~ i~ewood ~l3ed ~, by its ~er~ ure1 co~r~;n a m~ltiple o~
t~s silica g~ity is i~s a~.
lQ (Com~arisoll e~ample~
Ly liq~d s~speDsio~ o~ 4% ~msd ~ilica iIL ~ate~ ~tho~t ~he described ~icl~e~g additi~es was nsed for ~t:~s~ing a ces~
fi~e of l~ A Cl~e 13sa~le 8). Com~red wi~h w;a~ loIIe~ only htly le~ kened ~3~;pe~io~ W ~33ed ~n orde~ tv ac~hie~e the sa~e e~i~gui~i~g ~esult. ~he ~mbe:r of reignitio~ obtained was co~arable ~eo ~hat witih ~ aloIIe. T~i~ shows ~ ~che ~ood e~iT~ sh~g e~ect i~ depe~deD~ on the ~reseslee of a Jchicke~ed, aq~ ~sio}~ o~ amorpho~, sy~t:he~ s~l;ca.
E~le 11 500 ml of a~ appro~cel~ 32 gilica sol was prepared ~rom a sodi~m :
s;~ sollrciorl by ~re~lrin~ w~l:h a stso~g, add cat:lon e;s~a~er. ~ -The pEt o~ the. sol ~as appro~tel~ 5 and ~ e~posed ~o a ~;he~
action i~ a blenae~ for ~ ~tes~ uffered nv ~i~ib1e cha~ges~
~tar adding 2Sl of a 202 go1~et~y1e~e i~e solu~-lo~ er ar~
~e ~1endi~ there wa~ te thic~ g of ch~ 1;ca so1, ~ithou~ so~ gi~g to a gela~i~ous mass, had a ~iscod~ of 20 9~coD~d~3 in the o~tflow ~ y5 ~emiqlned sprayab1e a;lld adhered to ~r-~es. ~ er reyeated sheæ~i~ in ~e bleD.d~ l:he ~scosl~ ~2s ~til1 14~ èconds. l~here would co~sequent1y ap~eae~to b~ ~ s~ht t~ot:co~y, b~t -~ is not ~sadYasL~Lgec~s ~or ~pra~
:
500 }D1 o~ ppro~ 7~ si~ca sol ~ELS prepared ~roD~ a s~di~m s~cate so1ution by t:reat~g ~ a st~o~g, ac~d c~ion e~ ger.
l~e pE o~ ~e sol was app~o~imatel~ 5 The sil;ca sol was le~
- l2~9~7 to s~d i~ order to ~;el a~d the resull:l~g gel ~s stored for 2 we~ 3Z sus~esLSion ~ wa~e~r was t~en prepased isl a bl~nder, which wa~ ~prayable and ~ad ~ood adhe~ion actiosl. Its ~nscosit~
was 18 seconds in the D:~ cup with 4 m~ nozzle.
~'Pa~
A ~uspensio~ ~ o ~-1 a~pro~ely 2.5% ~i3ic~ conte~t b~ diln~i~g from an app~o~llatel~ 3% ~tlspellgion of amorpho~s si},~ca 1n wa1:er }~d ~ olltflo~r lriscosity o appro~tely 14-15 seco d~;. This 8n~-en~3ion ~as u~ed for ~ a stalldasd ~ire of C:_a~ A. Tne n~:eæ3~y e~b~g ~gellt quantity 7~s 1/3 of ~a~ of water ~sed ~.c the com~ on e~i~ g agent alld t:he n~nber of rei~
T-;$io~s ~?C hal~ed comp~red with w~Lter. Ther;e~ore l:he a~tlon i~;
m~ch better tb~ wzter, ~ o~ quite as good as ~hæt of a ~hicke~ed a s~pension S~ to 2.5g a:E~d prep red from ~ f~med silic~ accn- ~:
rd~ to E~amp~e 7 ~red~ctlo~ of ~e e~g~is~g age~Lt ~ ity com~ared with ~at~r to appro~ l4, rei~t~ons 1/4 co~ sed wi~h wa~er) .
, A ~spe~rion of 8g o Aero9il 200 ~as prepared i~ 150 ml o water a;~d of this 80g ~e m~:~ed wlth 35g of pro~lene glycol (~ d . ~:
69g ~ h 46g of propylene gl~c:ol ~B). A 2~d ~ were ~ e~ case t lcke~ed b~ ~dd~g ~ r droys of polyo;~ye~ e la~ryl ether.
Bo~h ~e ~o~ed or 4~ ho~rs i~ ~he rei~OEator at -12C, B appe-ari~g thic3c~va~le ~nd ~ tl~ck-l3gruPY. Ai~ 5 ehe t~icke~i~g obtailled ~ter addin~ the ~e3~ e ~me as ~eore freez~g~
l~a m:L o~ a t~kened ~spe~sion af 3~g ~ilica iD ~ter accordi~
to E~le 1 were ~aced ~h 5~ of ~odil~m hgdrogen ca~bo~ate. l'he o~lo~ viscosi~ ~s ~0 ~eco~ds ~ ~e ~)IB C~Lp ~4 mm). 0~ spra~g 2101~7 on~o hot s~rfaces, this ~;~ture re~ealed good ad~es~on character-istics. On e~aporati~g t~e w~er there was a strong gas e~olution of ~~ner b~b~le ~t~re th~n i~ ~he ~ase o~ the e~ting~ishin~ agen~
wi~hout sodinm h~drogen c rboDate. ~fter add ~ potassiu~ hyd~oge~
carbonate a simil æ resul~ was found a4~ due to the hi~her solu~ility up to 34~ co~ be di~sol~e~ he s~spe~sio~. The o~t~low ~i9cos-ity in ~he DIN cup waS 35 seconds. The p~ o~ theqe ~ ules was 8.o. It was fo~nd ~hat t~ sprs~ed o~ larers re~ined moist or a lo~ger t~e.
6g of Aero~ll 200 we~e s~E~e~ded i~ a sol~tlon o~ lOg o~ ~otassi~m sulp~te i~ 1~5g o~ water a~d the res~lti~g higbl~ liq~id s~spension was mised wi~h z few drops of pol~o3yethyleQe laur~l e~hes and stir-red. The resiltin~ ~hi~ked ~g led ~o ~n o~lo~ Yiscosit~ 0~ 20 se~onds i~ ~he DI~ ~up ~4 mm).
~ith regards to the additi~es in sa~t fonm described i~ Examples :~
15/1~, it is pointed out tha~ these mist~res do not act ~ rheopec-ti~ maD~er~ bn~ ehat with ~i~o~ous s~ear~ng are not ~hîsotro~zed to snch an egte~t tha~ ~he a&es~ ~ctio~ t~ ~rfaces i~ sig~ifica~-tly impaired. ~owe~er, on ~rayi~ on walls ~here wa~ mose marked ing wi~h th~e mi~t~re~.
~ '.
83g of water ~re blended ~ith 7g o $~med silica a~d O.lg o~ poly-ethylene ~m~ne (or the sa~e qua~ti~y o~ fat*y ~lcohol poly~lyeol ether o~ molecalar weight ~00, f~tty a~id pol~lycol e~te~ of molecolar wei~ht ~3~0, polyo~yethyle~e sorbitan mono-~atty add ester, or polyeth~len~ glycol of mole~ular we~ght ? 70~ and m~xed by s~irri~ he resul~ing p2~e was ~ ed ~n~o ~ plas~ic bag.
The ~ickness of the ~h~ pr~d~ced ~u~h~on w~s ap~ro~mately 8 m~
: . . , . ~
'-- 202la~7 ~n~ the dimension~ were appro5imatel~ 10~10 ~m. Cable ~ortio~
of dif~erent diame~er~ were placed o~ the cushion. A horizontal, 3 cm ~de! ~ap was colrere~ by said c~hioll. The gap was ~hen s~b~ect to flame ac~io~ rom below wi~h a ~as b~r~er. Tem~erzture~ of ~pp~
ro~. 700 & OCCU1Led on the ~der~ide of the c~h;on~ After a~pro~.
20 ~l~o flame a~pli~a~ he cables were undamaged.
~ .
cnshion as desc~i~ed ~n E~ample 17 was prod~ced ~ith an insert ~rom ~ pla~tic ~rati~g. The cus~io~ ~as pso~ided with ~el~ro strl~
clo~nres ~t thR ~d~. The resulti~g ~Qshion was placed ro~nd a polypropyle~ pipe wi~h a di~meter of 40 mm accordin~ to DI~ 1~5~0 z~d closed in the man~er of a slee~e ns;ng the ~elcr~ b~nd. The th~s protected pipe pa~t ~as ~ject to ~ ame action from below by a petrol-produced firP, so that the flames mo~ed passed both sides o~ ~he pipe o~ sleeYe~ Ihere was ~o damage or so~ening of ~he pipe ~ter 20 mi~teS~
~ample 19 A c~hion, as de~crlbed i~ E~amp~e 17 was ~illed w~ a ~aste ~ving a~ additio~ of lOg of s~ar di~solved in water~ The ~ushio~ w3s ~n~ u~ verti~ally and ~ubject tc thc ae~ion of a gss burner from the ~ront. ~ cable loc~tsd bebind it was undama~ed afte~ 20 ~ tes.
A falli~g apart of the c~s~ion a5 i~ the c2se ~itho~t a su~a~ addi-tion, did ~o~ occ~r due ~o th~ carbo~ ~keleto~-fo~m~g 3u~ar.
E~mple 20 10~5 ~ of a precipi~atio~ silica were suspended ;n 150 ~1 of wa~r.
0.2g o~ pol~eth~lene iml~ie were added to ~his highl~ l;quid suspe~-sio~, followed b~ vigoro~s ~tirring~ The s~s~e~sion -~^~ckened ia~d had a~ o~Low YiS~osi~ o 18 seco~ds.
.. _ . . _ _ . . .... ... .
..... ~ .. . . . , . , . ,, ., , ; ; . ~ . , ., . - , , ~ , r.: ~ :
2:l~19~7 - ~1 -~ele 21 5g o~ be3l~o~e (Eor~ 33:-~ or ~: 129-:E[, t~ademark o~ Ambe::ger ~aol;nwerke, ~mberg, Ger~a~y, or ~entoni~e D~B g) w2re s~spended iQ 2~0 ml of water, accompa~ied by stirri~g with an electrical g~ir-rinæ rod. ~o this highly li~id ~spen~og ~ith a viscosity of 11 seconds ~n ~he DIN c~ (4 ~m~ WOEe added ~.7g of a 20~ polyethy-lene ~mi~e ~ol~on i~ watPr, follow~d by stirring with t~e ~tirri~g rod~ ~he o~t~low time i~ the 4 mm DIN cup was then 14-15 secc~ds anh the spraying and adheslan beh~v~o~r wa~ ~ood. 0~ hea~ the ~pr~yed sJr~ees no ~dhesion problems occurTed ~nd a large 2mo~t of steam wa~ ormed.
~!æa!~
As ~ample 21, b~t ~siD~ 3g o~ beQto~ ~e. The out~low time was 13 seconds a~d the O~p~ay~g behavio~r good, the adhes~on behavio~r ~o cold sur~aces satis~a$tory a~d o~ hot sur~ae~3 goot.
~ZE~ Z~ ~COmp~rison e~ample) ~ike ~ample 21, bnt accom~an~ed b~ ehe addition of 20 ml of 2 mi~ture of 1~ of ~nar O~o~ ;n 100 ml of water. There was only a ht thi~ken~ng ~ction and 8 dea~ a~eous phase separated on ~he bot~om of the cup~ Guar xmm alone does ~ot act a~ a thicke~er i~ the case o~ the pre~e~ lo~ benton~t~ con~ent~aeion~.
... , .. ~
.
in agrlcult~re. The prepara~on of ~ch thicke3~e~ special e~
s~i~g ~g~nts generally regn;res special appara~ d par~ læly this a~pl~es wit}l res~ect ~co ~he ni~g t~:Lereo~. ~Che~ ~ general not be ~pplied ~ing convention~l fire e~nis~;ng sy~inges ~nd e.g. ~ ~e case of algina~e g~ms do not ~aYe 23~ op~imum ~d}lexing ~ction ~o ~e suri~aces follo~i~g s~pray~ng, ~articr~ y ~de~ thé
action of heat, ~he~ freque~tly c~e their use cha~acte~stios sfter eveIL a shor~ ~torage period a~d, a~l:er d~il~g, sometimes leave beh.r.d d ~ ficulty removable resid~e~3. .
The prepa~ation of a thicke~ed e~tin~uishin~ water ~ithou~ these disadva~ta~es, p æ ti~ularly a non-1ammable thickening age~ for the water in order ~o ;mprove the wa~er e~ti~uishi~ ac~ion9 is ~herefore highly des~rable. A~art rom ~he posit~e e~ects o~
adhesion to soIfaces, e~en i~ the case of e~e~ated temperatures, the formatio~ o co~esive 8~tin~ulsh~ ag~t ilws with 2 partic ly high wa~r percen~a~e a~d ~fie~entl~ high stability~ ehem~
ical and phy~iolo~cal ~ompa~ibllity with all dead a~d living mR~er-~al3 oecurring d~liLn~ th~ extin$uishing proces3, t m~3t mai~taîn its Use properti9~ eve~ fter prolon8ed storaQe a~d, if ne~es~ry, .
m~ be~;p~e~a~bI~ iQ a rapid, ~^~espen~i~e manner.. b~.m~ ng with .. ... !-'~
ordilu~r~ wat~r nd ~nst be appl_able ~si~g conventionally a~ailable flre e2tinæ~^shi~g ~qu~pment~ At ~re~ent the~e îs no ef~icie t fire e~tin~ui~h~3g age~t7 which s~îs~ies all these requ~^rements.
Ce~;n o the requisite cha~ac~eristics such as a broa~ compatibil îty w~h li~ d dead material are ~.g. f~lfil~ed ~ omo~pho~
. .. -. -. . - . . - . . . - -A~
2 1 0 ~ 7 .
~l;ca or s;1icic a~ , so that the l~tter i~; no^c onl~ widely us~d as a thicke~ ag~t ~cf. U~ln~ns ETlzyklo~adie d~ Tech~ische;~
Ch~e, 4th edit~oIl, Vol. æ, p. 473; 1~ k ~ e~ c~rclopedia of Chemical Te~hnology, Vol~ 20, p.778j E. Brunner, D. Schut~e, Chemiker Ztg. 89, 1~5~ pp. 437-40; H~ Fratzscher, Farbe u~a Lack, 75, l~69, pp. 531-53~). It ha~; a pa~ic~la~ly mar~ced t~bicke~
action ~n the form of ~med 3ilica ~re~ed by flame hydrolysis in non-polar 1ia~id~. In polar l~quid~ such ~s water the ~hickeD~ng ætio~ of said silic~ is less prouo~c~d, so that it ;q ~ecessary to ~dd relatively large q~n~ities for obtai~ing a si~nific~t ~hick-~ning action. It is aS ye ~Ot kno~n ~o use 3;Iicas in ~he ~orm of an a~eous s~s~e~ion fire e~t~guîshin~ a~en~s. Fumed silica tæ o~ly described a:3 a pulre~en~ speclal e5~t;ng~isn;ng ~ t for ~ ~ial ~ire s~Ltllations ~EIIB 0339 162 Al ox }~I}B 03~ll 006 ~l). A~
a ~esult o~ its e~:~reme ~ ness7 its general ~se as ~n esti~ui-shing age t iæ not p~sc~cabls.
I e.g. ~umed c;l~ca is sus~ended in water, mnch ~ore ~an.10% is ~eeessary in oraer to obr?~n a usable th~ckeni~æ ~nd th;s suspension also beha~es i~ a ~ otropi~ ~anner. This is a ~is2dv~ntage for u~e with standard fi~e ~tinguishi~ ~qui~ent. ~ e.g. a 5~ su~pel-slon o fumed sil~ca ~ wat~r ls spr3~ed ~rom di~ferent ~praying means, li~uids ~ass1n~ thinly out of th~ nozzles are alw~s obtained ~nd th~y ~u~ o~ surface5 i~ the same way æ wate~ a~ti~8u~shi~g comparison tests o~ gtand~aiz~d ~ises, su~ un~hickesea ~iLica S~BpellSlOng ha~e no better aCtio~ than water, . ~ , .
It ~s alsoAk~own~`th~t suspension~ o ~mor~houa~s~h~G~c.,sil~cas i~ wate~ oves a period o~ tlme (~e~erall~ w~eks or ~o~hs) sl~ly have ~ te~de~c~ ~o the a~lo~esation of particles 2nd to settli~g phenoDie~ owe~e~, this n~c~en;r~g effect~ is ullimportan~ fos the prese~ set proble~ as z resnlt o~ its slowne~s and limited e~ent. Ihis process, altho~h it can be accelerated so~e~hat adding electroly~e~, d~es ~o~ sepresent a sol~tion o~ t~e ~re~en~
proble~. S~k suspe~sio~ ~hickened by l~a~ing ~o sta~d also bec~e ` ` 21i ~1~4~
hi3hly l;q,~id a~2:~L ag ~L res~lt of 9tir~i~g follow~g p~olo~ged storage, i.e. whe~ aying us~ng conventional fil~ e2ti~guisher s~r~Lges said tl~o~ropic liq1lef~c~ion ~ aisadvan,,ageous, beca2lse ea~ly i~rpair~ ~he adhesion of the water e~i~}ce~ed i~ way.
~s shown, an e.g. ~ suspeD~3ion o~ umed silic~ water, followi~g thick~ as a res~lt of ~to~age, beeome~ highly ~ id ag:~;n on sprayi~
The ~roblem there:Eore arise~; of ~rov dis~ impro~ed fi:re e~ting~
uish~Dg agent of ~he ty~e o~ a thicke~ed extinguishi~g wster, par~i-c~larl~ ~a~i~æ an only l~mi~ed ~el~ht perce~tage o.~ s~nthetic amorph-ous 5ilica or oe~er, ~on-1~mable, broadl~ compatible minerals ~n the ~o~m o~ a 5u~pension in w~r s4 as to ob~n a th~ckenin~, whi~h takes place ~nsta~taneo~lY and ~ a ~o~rollæble ma~ner, gives ~ ~ea~y defined a~d s~able fin~l state and ~s not so thi~o-trop~ed by the spraying process th~ its adhes~o~ ~c~io~ p~i-red. It must also be ~sabl~ with oonve~tio~a1 ~ir~ e~ guishe~s and it5 pre~aration must not require 9pe~i21 eq~ipm~n~, whils~ havi~
a g~od adhe~ive action to bo~h ~r~.~.l and dowawa~dl~ directed smrEaces, espedall~ at elevated temper3tures. I~ particular, its e~tin~ h~ng action must be far superior to that ~f water.
~ccordin~ to the in~en~io~ this problem is solved in rh~t a th;ck-ened su~penYlon of amorphou~ gynthetic silica ~n ~ater is prep~red by misin~ erulent, ~umed sllica with wa~er and 2 compo~nd o~
the tgpe o~ a ~olyethyl~e glycol with a molar mas3 of ~700 to c600,00n7 deriYati~es o pol~e~h~le~e glycol ~uch 3s e~hers wl~h fatt~ alco~ol~ stér~ h fatt~ acids, ether~ w~th ~ar~ohydra-tes of molar masses 300 or blgher, ~s well as ~;th polyethylene ;mine, l~e necessary sil~ca concentration~ in wat r are ~ery low.
The~ only represent a ~r~etion of the amounts ot~erw~se re~uir~d f~ ~h~cke~ng ~n aq~@ous s~qpensio~, nsmely 1 to 7w compared with . .
~10%~
`` -~ 2~ a~
~e said additi~e~3 ca~ be added to t~e h~ id su~ ion of Si~iCZL ~ water, to the actu~ ates, bu~ can also be dr~ prPmi~ed with ~e siliea. In ~11 cases ~ eo~sly ~sable, ~ickened e~ ;ng w2ter 1~ obtained, which ca~ be ~ her tbickened i~ co~trol:Led m:lnn~r~ e.~. ~y the shear~g actio~ present ~ a fi:~e e::tingui~hi3~ pUIlly~ o~t ~y ~pai~ g o.~ the spra~ing ~ acit~.
On t~e ~:on~:r~, as a reslllt of the flow ~ ac~e~istics obtai~ed o tl~e th~s tbi~kened e;~ ~sh~ng wate~, co~p~red ~rith co~ntional water7 it~3 s3~ra~i~v cha3~acteristics a~e ~mpro~ed, e.g. wit~ respec~
to l~he range or lo~er :Erietional los~es.
The la:;t process caIL be referred ~o as rheope~ A.~ the additio~
~hiclce~ng ob~i~ed he~e ~ no~ los~ ag~i~ when che ~ea~i~ action is stopped, refereslce co~ld be ~ade ~o a~ ~irre~ersi~le rheo~e~y".
A~ a result ~e ~3e ~ tlle presently descri~ed ~icls~ned s~spension of ~morpholl~;, ~ Lthetic silica as . fi~e e~ti~g~shing agellt is p OE tic~larly sY ecti~e, beca~se 1~ a ~ery shorr ~e with a normal e~nO~u~sher 12sOe sa~aces can be thickly co~ered with the ~ighl~
ef~icient e~tinguishing ag~nt, no matter ~rom wha~ m~terial they are made or whicl ~eometrical ~o~it~on they ~e. ~de~ ~he action of heat ~he~e 1~ no decom~o~itlo~ of 3aid coatin~, such as a sofee-ning or ~l~pping o~ ~p to the drying of the wa~er.
The wz~er thickened i~ ~he ~bo~e manner bas a n~mbar of essenti.l advantages~ s~ch as ease of 3pr~yi~ or spr ~ g by means of ~a~i-0~5 type~ of fire ~tin~oiahing ~mps or ~yTinges in accorda~e with DIN (b~cket s ~ e/TS 2tS), a~ well as b~ me3ns o a hig~ ~
pres~re pump ~ing 'a working pressule of 100 bar, ~p~l~cability ~rom ~nd f re es~i~gnisher~, ~dhe~ion o ~ven thick e~tinguishi~g a~e~t layer~ of se~eral ce~tim~tres up to the evaporatio~ or drying o~ ~erti~al a~d doN~wardly directed surfaces h~ng differe~t Ghara-ct~ristics a~a mzde fro~ di~e~ent ~ater~alsO ~$ the ead of the Lire ~iO~hting me~sures the esti~gui9hing s~ent can be e~s~lg ~emoved in dama~e-ree ma~Yr ~om the s~b~erates ~n questio~J e~8. b~
` ~@1~7 s~raying off with water or by suction ~i~g conrentional ~nduclt~ial sllction eq~ipment. As ~e t~ickened e~i~ ish~,~,g ~ter i.s uot los~ thro~gh ~n~ away, it c~ be taken up a~n ~ollowi~g t~e e~tin~ishinæ process, s~ ~t co~ation of the ~ iro~ment by produ~ o~ ~ehe f~xe ~lowi~ awa~ with che e2~in~ishi~ water aIld also ~ater d~mage to b~ildi~s can be l;~n;ted. ~er dryi~g the ~i1;ca ge~ left b~ d b ~ ~d~orbi~g ch~racteristics, whlc~
~a~ also be ~ræ~tageo~s ~or ~kn'ng up decompositi~n products of the fire or other con~ auts.
It i~ par~l~ul~ d~a~tageo~ to ~tilize t~hi.s ~oper~ of ~he fir~ e~ iS~iP~ ~ge~t according to the ln~e~on by sucki~g in the dry pre~ix o~ the amorphous sili&a with the thickener i~ ~
e~$ing~d~;n~ water flow, ~e desired t~icke~m g taking place ins~an-tsneously. It is noteworthy that an addition o~ sli~htly more t~n 1~ o~ e.g. ~med silica to th~ ws~el is adequate f~r ~his p~rpose.
For cert~in applic~t~ons i~ ~zn ~l~o be advantageous ~o ~se large~ -3ilic~ q~ ties ~n ~ater, e.~. in orde~ to form with the e~tingui-shi~ agent a b3rrier ag~;nst the u~controlled flowing out of l;q~ids ~o~ the ~e areQ or the ~cki~g up ~ction o~ ~he sili~a for a~
cont ~ n~s present~ ~bo~e 7% silica i~ the ~ater w~n usi~g con~e-ntional e~ing~i3h~rs no lo~er a~plicabl~ pastes form, but these ~a~ be ~sed ~s ~ire protection masse~, beoau~e the~r ~om4geneit~
i~ ret ~ned even w~en there ~s a high water content and a low silica co~tent. A silica ~el obta~ned f~om water ~lass b~ neutraliz~ug and washi~g or by ion e~ch~nge and given a pas~y cetting is o~ly homogeneons for a ~hor~ eim8 after ~r~paratiOn a~d then q~ie~
staxts to gi~e of~ water i~ e~nsiderable ~uantities. Tbe ~ire prote~
ct~on mass prep~red 2ceordi~ to ~he inYention avcid~ ~his ~heno~e~on in the case o ~ h;~ w~t~r and low solid percent ge. These flre ~rotection masses are s~i~able ~n nmmerous wayæ fcr preve~t2tive fir~ protection for flammable str~c~res, in fi~e-retarding barrier ele~ehts or ca~la lines3 p~l~iColarl~ thos~ w~ich are seDsiti~-- 72~~9~
to corroslo~, fire decom2ositio~ produc~s or o~tflswin~ water.
me "thickeni~g aaa~ es~ used æcord~38 to t~e i~vention are ~qui-red in ~11 cases i~ only extremel~ ~mall weight co~ce~trations.
~ith the pref~rabl~ ~sed progortio~s of only 0~003 to 0.2%, ~ased on the total qu~ntity, they 3le soarcely ~oticed. Seqeral o~ the thick~ng addi~i~es described are con~ent~onalt~ ~lsed 35 emmlsi-~iera, eOg. f~r ~reases, wa~es or as spe~al sur~a.:tants. The "~loc-cnla~io~ o~ silica b~ polyglycol is co~sidered usef~l e.g~ for ~ater puri~ io~. It c~Dnot be co~cl~ded ~ro~ P~t;ng teachi~gs ~h~t a suspensio~ of ~ a or bentonite of abo~e 1% i~ water ~aQ
~uaaenl~ be made ~o uniforml~ ~hi~ke~ ~hrou~h the ~dicated compaunds of ~olye~gle~e gl~col~ o~ h~d~o~y~thy1~ted fat~y a d d, ~att~ alcohol o~ sug~r derî~ati~e~ or pol~e~hyle~e i~i~e, i~ ~e case of the sDall-e~ weight percentage~ ~hereoC and ~hat the th~ckeni~g actio~ obtai-- -~ed c~n be maint?;ned ~or a ~lmo~ unlimlted tim~, so that the eh~s obtained e2tingnishi~g agents ca~ be s~ored or ~s~d i~ s~atian-ar~ e~ti~gu~shi~g e~ip~e~t~ o~ tha~t the she~r actions occurr~
a~rin$ e~inguishin~ do no~ act i~ ~he form of a thi~ot~opizl~g and insee~d prod~ce a type of "irre~ersible rheope~izingn, which greatly ~a~ours the use as a~ hing ~ge~t by produc~ng sta-ble, adhering Wat~r layers. Thi~ i~ surprislng beca~se the aore-me~tioned compo~d~ OEe not o~ the co~ention~l th~ckener ~pe.
It is also indicati~e or the present inve~tio~ the described thickaning no lo~e:r OCClIr~ a~ co~eeIItratio~ls o~ ~he ~ i.c~cen~ng addiJGLve~ of the polge~er ~ype ~bo~e c~ lim~r.s t ~ t .5~) or t~L~ ~e addi~ion of concen~rstions a~ t~ickeni~2; additires of the polye~ier t~l7e abov~ these v~1nes to already ~c~cened ~pensioLs brings abo#t ~ r i~nmediate ~d ~e~ent dil~tion o~ thinnin~r 0We~6~, thi9 iS not a problem in ~ractice, be~ 3~ addition be easily n-~ored.
A~ incre~sed plI-~alue has a simi:Lar action o~ ~he efIec~ of ~h~
pol~ether type ~clcF~n~n~ age~rc. ~$ pE~alues abore 8.6 ~here iæ
-8 2~Q19~7 a reliq~efaccio~ of already t~ickerled suspensio~s, -~ich ~ ~1so ot ~sad~ eous, because ~or the e ~g handliIu, oi~ the e;cti~
uis4i3~ ageslt the pH~val~e is chose~ as close as possible to the netltr~l point. C~30ne~ts æ~i~g i~ a hi~ly ~1k~1ine ma~ner can conse~erltly not be added ~o ~e ~hickened ect~ g a~e3l~ form-cio:Qs whe~ ~s~g polyosyeth~le3~ derivati~es.
Tr~ the case o~ ether~ hieke ~ g ~dditi~res a~L e~ception is fonmed ~y compo~Dds h~ViD~ a weak alk~line ~ction suc~ a3 bi~arbo~-ate~. They are compati~le wi~h the ~hicken~d s~2ensio~s of amor-phous, sg~thetic ~ilica n a~y 501ibl9 co~c~ntration. For e ~ le, potassi~m h~dro~e~ carbon~te can be ~dded up to i's saturat~on conce-~tration o~ appro~ately 34%. Duri~g e~ icarbon-stes can decompose, accompa~ied b~ ~he rele~se o~ c~rbo~ dio- de, which incre~ses ~he e ti~iS~iD$ actio~. The suspensioD~ of a~or-phou~, sy~the~ic ~q~l;ca thicke~ed accord~g to the ~nve~tion ~re also compat~ble ~ith other, not stroDg alkaline sal-~s, e~g. ~rep2r-atio~ oan w~t~o~t di~icilty take place wit~ sea ~a~er, or pota~sium solphate, ammon_um phosgha~e or boric acid ca~ be d~sol~ed i~ the th~ckened s~S~Pncion~
Wkereas the thicke~ing addi~i~e polyethylene ;m;~e br~g~ sbou~
a stable ~hick~l~n~ action in the squeo~s silica susp~nsion i~
alkaline range~, the~e i~ a reliq~efac~ion in the strong a d d range~
In a~ ca~e, acid conditio~ are a~oided to pre~ent cvrrosio~.
~ow~er, if necessary, a com~ination o~ ~h~ two ~hi~keniDg addit-ives is po~s~ble a~d then, as desired, ~h~ck~ning can take place ~ ed~ther ~he acid o~ ~e a~cali~e ra~ge~
~ .
T~e described t~ic~ening e~fect is partic~ ly mer~ed With f~med silica. ~s is shown in the e~amples, i~ the case Oc precipitation silicas the nece3sarg co~ce~r æio~s for obt2iDin~ æ clear rhick~
2re m~h higher (5 to 15~) and the aah~sic~ actio~ ~s less satisf æ -tory. ~we~er, precipitætion silicas are less e~pensi~e ~hsn fmmRd ,, , . _ ............................ .. .. .
,.~`.',. - . ' ' ' ':
' ..................... . ' ~ -`.-.: :' -- . , 2~01 ~
_ 9 _ silic~:.
e~pensire b2se could be p~o~ided b~ silica 501Q e~g. ~repared by ne~raliza~on from wa~er glass, ir it was po~sible to pre~are therefrom w~tho~t grea~ time and ~roc~ss e~pendit~re a homogeneo~sl~
~hlck~ed s~spenslon. Although s~lica sols, if the~ ~e not ~abili-zed, ha~e a tende~cy to ~elllng~ i.e. to the form~tion of a cohesiye gelatino~s mas~, the latter ;~ ~ns~ltable ~or ~he presen~ ~et ~rob-lem, becan~e t~ere iæ a poor ~dhesiPn: to surfaceq a~d o~er a period of ti~9 it ~eleases the w~er contained ~here~ and grad7~ally also h~sdens, T~elr ~ ticles ~e ~o~ ~e~erally displaceable agal~st o~e ~other a~ t~e ti~e of ~o~stio~, i.e~ ~o flow ~haracterl~ic3 e~ist. By d~persi3$ s~ch sil~c~ ~D~l~tinou_ ma~Ds it is ~lso p~sgi ble eo prep~re thi~ke~ed, aq7teo~s ~lica ~nspensions partl~ suitable for ~ire e~tl~g~isbi~g purpose~ is ~lso possibl@ to lea~e the relati~ely lo~ salt co~tent present i~ the ~ase of 2 ~sa~le thi~ke~-ing in a~cordance wi~h ~he ne~trali a~ion process 2~d this does not impair the e~tinguish~n~ ac~io~. rhe thic~e~d su~pensi~ns o sy~thetic, amorpho~s silica prep~red by means ~ neutrali~a~on processe~ do ~o~ behave ~u rheopectic manner i~ the same way as ~hoqe prapared _rom ~umed ~ilica~ Ihey are suita~le in ~h~se sit-natio~s, where the ra~d ~ncompli~ated preparation ~n situ or direct ~reparatio~ i~ the fire ~tinguish;ng process is not as decis~ve as the ~ g o_ ~ire e~tiDgui~e~s or statio~ar~ e~t ~ ishi~
equl~ment.~.
I~ solviog t~e s¢t ~roblem o pro~iding ao ~f'ect~re and w~dely co~patible ~ire e~tin~9~iDg agent ba~ed on a th~ckened ertingu sh~g w3~er i~ has been!~o~nd that~ a similar ~n~er ~o the sylthe~
~lc, amorpho~s cillca, b~ntoni~e, sta~ting from a hi~hly lig~id s~spension iQ w~t~ with ODl~ a limited eoncentrz~io~ can be rapidly ~d d~rably ~:o3l~er~ o ~pr~y2ble, adJ~ re, t~icke~ed 5usper~i-OD~3. This e~fect wh:~ch immediatel~r occ~rs with rgorous ~ir~g ~s not as pronounced as ~i~ :Eumed si~ he ~chicke~
2 1 O ~ 9 ~ I
. ~ -- 10 --additi~e~ de~ribed i~ the inve~tion the ben~oDite whi~h in low co~centrat~ons only produces ~h;n s~spensions can be con~erted in concentrat~o~ of l.~X in water into thicke~ed su~penslons in water nsa~le as fire e~tingaighing ~ge~ts and has a good 2dhes~vo action to sux~æ es. ~owever9 ~he s2me e~ect ca~ot be a~hieved with ~he k~ow& thicken~rs such 2~ gu~s, pol~a~rylamlde a~d the like wi~h mol~- ~asses of ~6ao,000, or g~la~i~, at least i~ the prese~tly described lo~ ben~o~ite conce~tx~tions~
~ithin the 5cope of the inre~tlon the stabi ~ ~ion of the deqcri~ed fire e~ti~shi~g a~en~s agai~9t frost a~tion by the additio~ o~
cQmpound~ of the glycol or gl~ce~ol t~pe ~s algo fo~nd ~o be advan-tageo~s~ Co~po~nds e~ecti~e ~or ~rost and oorrosio~ prote~tio~
l~ke borates, c~n, if nece~sarg, be ~sed. It has been ~o~d ~ha~
a sig~ificant atdition of these compo~nds ~o p~o~ect against frost does not ~m~ir the ~hicheDi~ ~ctio~ or 3tabil~t~ o~ ~he thicke~ed fire ~tLnguishi~g agents described.
~he ~oUowin~ esanples ~ strate the inyention ~ thout res~ricting . .
the same.
~mple 1 (general preparation e~ample) ~-10~ o~ ~omed oillca ~¢sco~l 200, re~i~tesed tr~d~s~k ~L D~uYsa, Gesm2ny) were suspended 1~ 190 to 196 ml a water, accompanied by s~i~ri~. The re~ultlng suspens~o~s sre hig~ly l;qu~d wlth p~ e~
o ~bout 5. If the~ ~re not stron~y s~rred, the~r ou~loN ~l~es in ~he DIN c~p ~4 mm ~ozzle~ OE~ ~ to 11 seeonds, ~t ca~ be ~p !.,,~'`,`.,:~'':::,.'~:.' .. '1 ~0 14 se~oads.~f:sli~ht ~gglomer~ion occurs. I~ ~t~rring takes . ~ o~
~l~ce with aQ elect~ical Btirring ~od ~appro~imat~ly 800 ~.p~m~), the~ become e~ more hi~hlr t;qn^d with a~ out~lcw time o~ 9 ~ecn-nds, ~om~arabte ~ith ~he ris~osi~Y of water. To ca~d s~s~ensions are xdded a ~ew drop~ o~ polyo~et~ylene la~ryl e~her of mwl æ mass 3ppro~m~ 380~ or a 50g aqueo~s solution of poly2~h~1e~e ~lycol 210~9~7 of mD~ ~ 4220, or ~ S0,~ aaueous solution OL polyo:~yet~Lylene so~itan mo~os~rate o~E molær ~ss 2~pro~Da~ly 12G0, or a conce~-t~a~ed solu.ion o~ ~120 jojo~z aoia and PFG-i~) "o~ob~ ~lcoho7 e cose;ly; or dot:ose~yl ac~d~ l~ohol ro~ ~o~obz oil i;~. ~tho~-,~lated fo~), or a ~ ?olyeth~le~e imin ~o7~ion (~ol~r~ ~, registOEed e~rad~-r~c o ~sASi~ I~.~osh~ e~, &er~zn~? ~"d mi~n3 ~lace b~ ~ rrirl~ ~ith 2 s~tu~a. .Ir. R11 C~3es ~ere i9 2~.
tely~ elearl~ no~ice~ble thickening to ~ ho~geneo~s~ ~iscous ~usp~:io;i w~. as3 ~ f~ctf.on o~ the si.7,~ por~ion, ~s preel7-qd ~o ~ ~raryi~g e~ent. ~lo~ t~ of 14 - ~ 35 ~ec~nd~
o~cu~, or past~ ~s~encies a~e pro2uc2~ wh~ not be deter7 ~ned ~n the o~"flow cu~, but ha~e a ~ood ~r2,,~rlg or adhesion c2~-ae~ , OrL accnrate ~ hin~ o t~e necessar~ um, au~ ities Of ~he ~dicated 2~aiti~e~;, it i~ fo1md t~at e~en 0.007~ ~35 ppm~
æe e~f~i~e, a~d ~.a~ in the ~se o~ ~olyo~e~th~lere com~o~nds ~ere is a~ m;,, ~ ap~ro~imabelv 1.5% in ~he o~e.~l., ~re, above ~ch r~ e~don oc~srs. If th.e l~.h~s o~t2i~ed, lo~g ter~
~-~able, t~ickened sll~persio3~ of s~lic2 undergo z~ eren brief~
rous stirr~g ~e.~ ~t~ an elee~ ,irrin~ rod?, t~e ~icken~g sig~i~icantl~ i~c_ eases Pnd re~ins ; n ~-; s 'or;~ t is e~sil~
~o~sib~e ~o spr2:~ these l~boraeor~ c u~n~ 2 s~ e bo-..le ~.ith or wi~out ~n at~zin~ no~zle. On ~ t all ~urf2ces, such as wood i3~ ~rea~ad or ~ ~shed form, plzstie, rubo~r, 8h8s ~.
metal tm~oblemati~l ~dhesiorl 1~ pa~s~ble~, e~e~ reater layer knesses~ out anv d~sadvanta~eous ~hange ta~ pl~c~ to tbe layer ~ ru~ng out. slidi~ o~ or w~ch ~n 2!1~ other wa~
~mp ~Ir~ the ~ire e:~tin~ actlo~ s ~n ~aF~icular ~plie~
to hot 3urf~ces, w~e~e ~ere ~ no sl~ding o~, ~e s~ ed or -~p~inkled surf'aces dr~ w~thin 12 to 48- hourrs; ~s ~ fu~ction of the - -layer ~ick~esses a3~d ambien~ con~iti~rls. The dr~, usu~ l~k~
like sil~a le.'~ b~.~d can eesil~ be me~h~n~c2ll~ re~o~ed ~om the s~2ces z~d c~a e~f~ be seadily b~shed ou~ ~ro~ .abric~.
21 ~9~7 ~a~Dl~ 2 (Ge3lerzl pre~aratiOn e~ample) 4--lOg o~ ~umed silicz ~re ~ed ~th i:~ ea~L c~se 0.3~ of polyo~
ethylene lauryl ether o:r polyeth~ene glycol of ~l~r mas~3 ~0 o~ polyetl:~ylene glg~col sorbita~ mono9te~;3,te (molar 1~1aS9 appro~-;m~tely 1200~ or PEG-120 ~ojoba acid a~d Pli~-l~O jojo~z ~lcohol9 or polyethylene ~ne, so l~at ~ d~ prem~ oL~ed. For this pt~rpose po~$ tal~; plae~ o~o 200 ~1 o: wate~, followed by m~
w:Lth arL electric 1 9~g rod (bl~de diameter 3~5 cm~ appros.
80~3 r.p.m.), so th~t pzst~r consisl:encies are obta:ned. 0~ addillg 150 ml oi~ water ~i~C0~:3 mspe~ons axe ob~ed ~ o~l ow ~i~cosity o~ ~4--30 seco~Lds i:n t~le D13!1 ~up (4 mm ~lozzle). The ~ara~
c~ tics of t~e res~lting l;hi~ d sil~ spensio~s, w~
are also di~ectl~ ob~i~ed by add~ the elrti~e 3SO ~1 ~o w~ter, relre 1 310 dife~e~ces compared with t~he su~pensio~Ls ~bta:~ed i~
comparable concentra~ioDg i~ ple 1..
100~ o:E a dr~ ~re~ of i~umed s~l~ca ~9?g) a~d ~olyo~yethylene la~l ether (3~) obtai~ea accordin~ to l~bis e~le are fillea ;nto a stor~ge ~ sel and, u~g a s~ction hose7 whic~ pipe connec-tion has ~ ~eed i~Lto a ~ ~ater 10w~ is s~lcked by meuls o~
a ~ ht vacuum ~nto s~id wate~ 10w, followed by m:L~i~g ~nd thic~
enia~, so tb~t ~ wator p~ss~g ollt o~ ~ ~lightly narrowed glas~ :
no2le only ~ ew cent~met:res a~ter the ~i~g point ~lrezldy has a~ escell~ dhesio~ to a g~ss su~ace. Fnr ~cJ~ng in the dry prend~;, it is al~o po~3sible to ~se the ~et~on side of a water jet pump ~nd the sur.king ~n of ~e ~lverlllent pre~ can be continned o~ a long time ~i~chout p:coblems or.blo~ es. 33g a corresporLd~
sion~g of ~he ~u~eiol~ eeds, reg~lating the ~ter ~alltity and ehe water pre~sure7 ~che ~;c~e~ ~roced~re can be eoll~rolled ~L t~e desired man~ ble thiclceni ng accordi~g to this proce~
dure is e.g. o~ ed ~ith a silica co~eent:~atiOn of oDly 1.3~ i~
water.
_ . , . _ . .. .. ...
21019~7 :e~3mple 3 ~ ddi~ gela~cin solution (which ha~ dy bee~ describad as predpitant for s~.lica sol, b~t ~ a we~ht ratio of ~lmost 1:1 ~y l'h~, Gr~h~m, Philos. Tra~Ls, I~don, 186~, pp. 2~5/6) a l~ keni~g of the ~med silica suspe~sion similar ~o 13;c2mple~ d 2 is obt~i-ned with low concentra~ions of e.g. 0~1~ ga1~ , b~t su~ suspens-ions reveal m:Lc~obi~l co~ ion a~ter a ~ela~-Yel~ ~;hor~ ~iod.
~! t~0mPaXi80n e~ample) T~e t~c:kened silica slls3~e~dons obts:~ned accordi}Lg to l~am~les 1 a~d 2 were miæed with in each case ~ sodillm ~bonate aIld bora~, so t}at pE-Y~l~es of 11 or 9.1 ~e obta~ed, ~ere~3 ~Le ~iclce.~g disappeared im~ed~Ltel~ ~er aaditio~ with 211 ~e pol70~yet~hylene de~ivati~e~, it rem~i~ed in 1:he case o~ a polyethylene iD~e thidcen-ed si~ca suspe~
E~le 5 (~omparisop, e~;ample) The ~bicke~ed silica sllspensio~s obt~;ned accord~$ to }~ample~
1 and 2 were nr~ced with ~n each case smaLl ~mo~Lts of hgdrochlo~ie acid ~ Lt~ a pE3: o~ 1 was ob~ ed, and ~i~h i~ esch ca~e ~% ci~e scid o~ a~cor'oic ~id ~ntil ~e~ g a p~ of ~ a~d 3. I~ the case o a~l pol~o~ethylene co~po~ds the thicke~ing waY ~ta;ned ~n these add ranges~ Eoweres, when mi~ed with poly~ yle~e imi~e ~ r~liq~e~ ion was obs~rved.
........ ~
le 6 (Prepara~ion and lls~ with a b~cke~ s~ 3e) ~6g of f~med siliaL were sti~red with 11.68 litre3 of w~ter. I~fter lea~ ng to st2~Ld for one hoar with occ2sional sl;~ ;ng, a viscosity o 13 seconds was mP~ ured i~ a DIN ou~flow cup. 35g o~ polyo~y-ethyle~e la~l eehe~ we~e added, acwmp~ed by ~ g, ~co ~is " 2~al~47 hioj9ly iir~d sus~enslo~. ~ e- e S~:or~ t e ~e ~scosit~ o the E~eure rose ~o a p2S'C~5 ..ez~''y s~irrable an~ uo~S~e cous~s;e~}c~.
10 lle~es of ~he ~hlls ~-c~en~ e3ri;~ishinc w~;~r-~ere .i~led into e ~c~c~t sy~ee a^~o~d~ to nI~' 14L.r~5. T~.o resul~ ic'~
er.ed esL;~ g ~d~er p~o~ed ~o ~e sp~a~able ri~h ~ ~ltipurpose ~e~ pipe 1~ ~c~ord:Lr.g to DIN 1~.~3S5, ~ D~inY t:he s~
process there was a cle~, fu~Lher ~hicXeni~g o~ ~e ~teri~1 p~S9i~
ou~ o~ ~ 3~t p~'pe a~ colDpare~ ~iLtn ~ Oduc~d ;-~o ~he btl~k2 syr~nae, ~e s~ra~ea maLe.i~ a ^~ersr goo' adhesio; to a ~OE~i-cal, ~ai~ed co t:rete ~r~ce ~ d~ng ~n?ll)~ er spra~il~ ap~
~ma~el~ S l;~res~ ~:he re~ in~ ci7e li~r~s lef~ !be~ d 1;~ ~e buc~et s~ e ~ere ~ ed with h~e same aol~n, Of ~ e by a~,~t~arL
~r~d ~he s~ra~n~ proce~s was ~ontin~ed. ~en with th~s redu~ion o~ the conce~stratio~ o~ the thicke~ed silica sus?e~sio~, a ~ood t~ll adhesion on s-or~ stil~ cc~urred~ her s~ in~ ~e~ts good ~dhesio-~ ~a~ ~o~d ~o ~rdboard, ~iood aDd ~ ftter lea~
ir.~ to st2nd f~r 14 m~nt~s, t.~ s~ a~oidi g eq~poration losses, no ~ettl~ng o~ -~e ~teri31 tH~S detecte~ z~d ~t co~-la ~ill be r~ad~t ~l~ spr~yed.
e 7 ~repa;zLion ard use t~h 8 P3~LCb1 WOE 31i~) 10 '~8 of fume~ si:L~ca wer~ st~rred i~to lS~ .res o~ water. Th~
r~g~ultln~ sus~ens~on coh~aine~ easily crus~le p~ c~es wi~h a ~a~eter of ~- ~o ~ ~, w}lich slowl~ sedimented on the ~o~.tom on lea~g to s~and. T~e sUpe~at~nt sus~ ion no longer l~ad ~y ~articlss and had ~Lhe c~a~acteris~Li~s o~ a clol,;~ silioa sol, uh~ch st~ on~a~ed 3 s~ ter lea~i~g. to :star& . ' or- 6 ~eecs t~alri-- . .. -: .~. --metric de~er~atio~ af~e~ dryi2g and 'æ~). The ri3co~ty of the sed~e~ted sil.ica sol w~s a secon~s in ~Lhe I;3:h' ou~ow cu~ a~t2r 6 t,Teelcs stor ge, but 11 s~conas ~i~ec-l~ fQlk~ ?reæ~a~io~, i,e, ~r-t1~ ~e ~ti~ s~s~ended ~ar~-cle~. S ~les c~ ~.~ sol cl~i-fieâ or p~ied ste~ s~t-1:~8 and thos2 q'C~ end.~d .
..
~la~7 matter w~re co~vertable wlth the additives ~eferred to i~ E3ample 1 and i~ the co~ce~trations give~ therel to a th~ckened silica s~speDsion. The still unthickened suspension wa~ stirred wit~ a padd~e mn~er a~d the res~ltis$ 200 litres were sepa~ated into two ide~tir~l pærts. ~he part was stored ln se31ed ~orm w~tho~t f~r~her addi~i~e~ far obserYin~ the lo~g term beba~iour. Over a twal~e month period rh~re was a slo~ ~hickening and ~ettli~g o~ ~he hottom oa lea~ing to stand o~ said ~ ca s~p~sion ~ot p~o~ided wi~h the iDdicated addi~ives. Eowever, it was still miable ~nd spray sble tbro~æh ~o Y-le~ a~d b~came highl~ liq~id ~aiQ by thi~otr~p-i2i~g. It co~ld be thickened by the additi~es r~erred to i~ ~a~ple 1 a~d conv~r~ed into a thicke~ed, aq~e4~ 9ilic~ ~c~speDsio~ bl~
as a~ adhe ~ fire e~ti=~cish;~g age~t. The oth~r par~ o~ the mis~re w~s mixed wi~h 250g of polyo~ye~hylene lauryl ether immediat~
ely ~ollo~in~ prepara~ion a~d stirred with a paddle ~dser, which led wlthin appro~ately 30 seco~ds to the ~ni~or~ icke~i~g of the eIItire s;~ usp~sio~.
The ~h~.~ thicke~ed eYtiDg~ishin~ water wa~ sprayed in proble~-free ma~ner as both a ~11 iet an~ as a spray jet ~siQg ~ portable po~er pump TS 2~5 accord~ng to DI~ 14410 with a mnltipurpose ~e~ pipe C accordin~ to DI~ 143~, part 1~ ~s In E~ample 7, there was a d ~ar further ~ckeni~ of ~he e2tinguishing w~ter by the pumping and 9~ra~iD~ proce~s~ Good ranges ~nd an e~cellent wall ~dhe~lon to ~ertical s~rfaces we~e obtz~d. ~s l~ Example 7, i ~ece~ry, further ~hlnni~g With watflr wa~ pos~ble Nhi1st maint~1nlnv the c ~ acteri~tics.
Ate~ se,:.the t4ickened, s~raged e~ting~ishi~g:::wate~ ~o~ld be taken~p ag~ln b~ shovelll~g or sactio~, so that ~ ir~ re3~lti~g p~od~-cts contal~ed therein only passed t~ a limi~ed e~t-~t, if at ~11, nto the so~l.
The eg~in~uishi~ ~ater ~rom ~his ~i~t~re ~hioken~l ~y ~d~;ng 2101!~17 -- lo --polyo~yle3le lauryl e:ster, like the silica suspP~sio~ withou~
the additive, w~s let to sWd for 12 mont~s. ~ re wa~ b~
tially no chan~;e ~o its llse be~our aIId ~o se~di~8 of residues c~ ~e bot~osll of the vessel. Withoul: preservative sl~reS, there were ~o cle~ar b2cteri~1 conta~i~R~cion phe~Lo~e~a ænd it mU5~ be ~o;n-ted out tha~ ~ sa~le used iIl an e~guis~ g test, which was COllt-nnn~ted b~ a cert~i~L amo~nt o:~ soil had, on the basis o~ its s bee~ conta~ated 8:Eter a ~ [owe~sr, ~o s~e~l pre~3er~
tio~ me~es ~re reqtl~red ~ he c~3e oi~ cle~ stora~se~
~e e~t~ishin~ test) 1~ tes~ re wi~h solid ~}elg o:~ fire Class A ~woo~ien cri~, 40~40 cm, 7 l~ye~s, ~reb~g ~e 4 m;n.) was e~lin~s~ed ~ith a ~pra~
iet ~ 7n~c7~ened e~ ;hi~g water, prepared æcordi~g to E~as;r ple 7 ~nd set to 2.5 aD~I 3% SîO2 coneeP.t. Co7~ ed with the ex~-g~.s7hi~4s te:~ ~th ~ater, fo~ ~guishi:n~ p7;~o~es oD3~y lJ4 of ~he e~ting~i~hin$ a~e~t ~ua~tity was con~ned ~d the Ilumbe~ o~ ~ ~
rei~tions decre~sed to l/4. ~thP ~dher:~ layer of thi~ened e~
gUi6h:1143 ~ates del~yed or preve~n~ed f~re ~ropaga~orL and i~ition of those p~ o:E the flammable ~erlal ~ot affec~ed by t~ fire.
The l~r~e allso~ of 5~eam fo~med reYeals t~ he r~;ckeled ~
ap~lied is al~ot3t ent~ely a~aîlable ~or eool~g and e~gt~ g R~cse~, beca7~se it doe~s ~ot ru~ o:E~ the b7~able 7~rts and ~nto ~h8 8ro7~d. l~e 8~3ent î~3 suitable fo~ es~7~g~ing f~am~able ma~er-ials s~ch ~ woad, pla~3tic7 ~bber, wooden m~ter~als, t~stile-s ~qnd othes orgaIIict :solid mBtf~i.al5.
(Fi~e OEt~i~ test) ~~ `: -`
13-A fi~e ~ccording to RFS ~423) was e~ci~;~ed ~ h an e~ctls~g-g wate:r form~latio~ pre~ared with ~ ~% thic~e~Led qil.ica su~pen-s~o~ accordi3lg ta F.~ample 7. e e~ gni.qh;ng a~en~ ~eo3~ io~
~ to co~plete es~ was only 1.? kg. O~ly 50~ of s~.l;ca ~, ... : . :: , .. ;. " ~ , .. . . .
2 ~ 7 ~e~e co~ med for comple~e e~g~ishing o the fire. The qua~tity o~ i~ewood ~l3ed ~, by its ~er~ ure1 co~r~;n a m~ltiple o~
t~s silica g~ity is i~s a~.
lQ (Com~arisoll e~ample~
Ly liq~d s~speDsio~ o~ 4% ~msd ~ilica iIL ~ate~ ~tho~t ~he described ~icl~e~g additi~es was nsed for ~t:~s~ing a ces~
fi~e of l~ A Cl~e 13sa~le 8). Com~red wi~h w;a~ loIIe~ only htly le~ kened ~3~;pe~io~ W ~33ed ~n orde~ tv ac~hie~e the sa~e e~i~gui~i~g ~esult. ~he ~mbe:r of reignitio~ obtained was co~arable ~eo ~hat witih ~ aloIIe. T~i~ shows ~ ~che ~ood e~iT~ sh~g e~ect i~ depe~deD~ on the ~reseslee of a Jchicke~ed, aq~ ~sio}~ o~ amorpho~, sy~t:he~ s~l;ca.
E~le 11 500 ml of a~ appro~cel~ 32 gilica sol was prepared ~rom a sodi~m :
s;~ sollrciorl by ~re~lrin~ w~l:h a stso~g, add cat:lon e;s~a~er. ~ -The pEt o~ the. sol ~as appro~tel~ 5 and ~ e~posed ~o a ~;he~
action i~ a blenae~ for ~ ~tes~ uffered nv ~i~ib1e cha~ges~
~tar adding 2Sl of a 202 go1~et~y1e~e i~e solu~-lo~ er ar~
~e ~1endi~ there wa~ te thic~ g of ch~ 1;ca so1, ~ithou~ so~ gi~g to a gela~i~ous mass, had a ~iscod~ of 20 9~coD~d~3 in the o~tflow ~ y5 ~emiqlned sprayab1e a;lld adhered to ~r-~es. ~ er reyeated sheæ~i~ in ~e bleD.d~ l:he ~scosl~ ~2s ~til1 14~ èconds. l~here would co~sequent1y ap~eae~to b~ ~ s~ht t~ot:co~y, b~t -~ is not ~sadYasL~Lgec~s ~or ~pra~
:
500 }D1 o~ ppro~ 7~ si~ca sol ~ELS prepared ~roD~ a s~di~m s~cate so1ution by t:reat~g ~ a st~o~g, ac~d c~ion e~ ger.
l~e pE o~ ~e sol was app~o~imatel~ 5 The sil;ca sol was le~
- l2~9~7 to s~d i~ order to ~;el a~d the resull:l~g gel ~s stored for 2 we~ 3Z sus~esLSion ~ wa~e~r was t~en prepased isl a bl~nder, which wa~ ~prayable and ~ad ~ood adhe~ion actiosl. Its ~nscosit~
was 18 seconds in the D:~ cup with 4 m~ nozzle.
~'Pa~
A ~uspensio~ ~ o ~-1 a~pro~ely 2.5% ~i3ic~ conte~t b~ diln~i~g from an app~o~llatel~ 3% ~tlspellgion of amorpho~s si},~ca 1n wa1:er }~d ~ olltflo~r lriscosity o appro~tely 14-15 seco d~;. This 8n~-en~3ion ~as u~ed for ~ a stalldasd ~ire of C:_a~ A. Tne n~:eæ3~y e~b~g ~gellt quantity 7~s 1/3 of ~a~ of water ~sed ~.c the com~ on e~i~ g agent alld t:he n~nber of rei~
T-;$io~s ~?C hal~ed comp~red with w~Lter. Ther;e~ore l:he a~tlon i~;
m~ch better tb~ wzter, ~ o~ quite as good as ~hæt of a ~hicke~ed a s~pension S~ to 2.5g a:E~d prep red from ~ f~med silic~ accn- ~:
rd~ to E~amp~e 7 ~red~ctlo~ of ~e e~g~is~g age~Lt ~ ity com~ared with ~at~r to appro~ l4, rei~t~ons 1/4 co~ sed wi~h wa~er) .
, A ~spe~rion of 8g o Aero9il 200 ~as prepared i~ 150 ml o water a;~d of this 80g ~e m~:~ed wlth 35g of pro~lene glycol (~ d . ~:
69g ~ h 46g of propylene gl~c:ol ~B). A 2~d ~ were ~ e~ case t lcke~ed b~ ~dd~g ~ r droys of polyo;~ye~ e la~ryl ether.
Bo~h ~e ~o~ed or 4~ ho~rs i~ ~he rei~OEator at -12C, B appe-ari~g thic3c~va~le ~nd ~ tl~ck-l3gruPY. Ai~ 5 ehe t~icke~i~g obtailled ~ter addin~ the ~e3~ e ~me as ~eore freez~g~
l~a m:L o~ a t~kened ~spe~sion af 3~g ~ilica iD ~ter accordi~
to E~le 1 were ~aced ~h 5~ of ~odil~m hgdrogen ca~bo~ate. l'he o~lo~ viscosi~ ~s ~0 ~eco~ds ~ ~e ~)IB C~Lp ~4 mm). 0~ spra~g 2101~7 on~o hot s~rfaces, this ~;~ture re~ealed good ad~es~on character-istics. On e~aporati~g t~e w~er there was a strong gas e~olution of ~~ner b~b~le ~t~re th~n i~ ~he ~ase o~ the e~ting~ishin~ agen~
wi~hout sodinm h~drogen c rboDate. ~fter add ~ potassiu~ hyd~oge~
carbonate a simil æ resul~ was found a4~ due to the hi~her solu~ility up to 34~ co~ be di~sol~e~ he s~spe~sio~. The o~t~low ~i9cos-ity in ~he DIN cup waS 35 seconds. The p~ o~ theqe ~ ules was 8.o. It was fo~nd ~hat t~ sprs~ed o~ larers re~ined moist or a lo~ger t~e.
6g of Aero~ll 200 we~e s~E~e~ded i~ a sol~tlon o~ lOg o~ ~otassi~m sulp~te i~ 1~5g o~ water a~d the res~lti~g higbl~ liq~id s~spension was mised wi~h z few drops of pol~o3yethyleQe laur~l e~hes and stir-red. The resiltin~ ~hi~ked ~g led ~o ~n o~lo~ Yiscosit~ 0~ 20 se~onds i~ ~he DI~ ~up ~4 mm).
~ith regards to the additi~es in sa~t fonm described i~ Examples :~
15/1~, it is pointed out tha~ these mist~res do not act ~ rheopec-ti~ maD~er~ bn~ ehat with ~i~o~ous s~ear~ng are not ~hîsotro~zed to snch an egte~t tha~ ~he a&es~ ~ctio~ t~ ~rfaces i~ sig~ifica~-tly impaired. ~owe~er, on ~rayi~ on walls ~here wa~ mose marked ing wi~h th~e mi~t~re~.
~ '.
83g of water ~re blended ~ith 7g o $~med silica a~d O.lg o~ poly-ethylene ~m~ne (or the sa~e qua~ti~y o~ fat*y ~lcohol poly~lyeol ether o~ molecalar weight ~00, f~tty a~id pol~lycol e~te~ of molecolar wei~ht ~3~0, polyo~yethyle~e sorbitan mono-~atty add ester, or polyeth~len~ glycol of mole~ular we~ght ? 70~ and m~xed by s~irri~ he resul~ing p2~e was ~ ed ~n~o ~ plas~ic bag.
The ~ickness of the ~h~ pr~d~ced ~u~h~on w~s ap~ro~mately 8 m~
: . . , . ~
'-- 202la~7 ~n~ the dimension~ were appro5imatel~ 10~10 ~m. Cable ~ortio~
of dif~erent diame~er~ were placed o~ the cushion. A horizontal, 3 cm ~de! ~ap was colrere~ by said c~hioll. The gap was ~hen s~b~ect to flame ac~io~ rom below wi~h a ~as b~r~er. Tem~erzture~ of ~pp~
ro~. 700 & OCCU1Led on the ~der~ide of the c~h;on~ After a~pro~.
20 ~l~o flame a~pli~a~ he cables were undamaged.
~ .
cnshion as desc~i~ed ~n E~ample 17 was prod~ced ~ith an insert ~rom ~ pla~tic ~rati~g. The cus~io~ ~as pso~ided with ~el~ro strl~
clo~nres ~t thR ~d~. The resulti~g ~Qshion was placed ro~nd a polypropyle~ pipe wi~h a di~meter of 40 mm accordin~ to DI~ 1~5~0 z~d closed in the man~er of a slee~e ns;ng the ~elcr~ b~nd. The th~s protected pipe pa~t ~as ~ject to ~ ame action from below by a petrol-produced firP, so that the flames mo~ed passed both sides o~ ~he pipe o~ sleeYe~ Ihere was ~o damage or so~ening of ~he pipe ~ter 20 mi~teS~
~ample 19 A c~hion, as de~crlbed i~ E~amp~e 17 was ~illed w~ a ~aste ~ving a~ additio~ of lOg of s~ar di~solved in water~ The ~ushio~ w3s ~n~ u~ verti~ally and ~ubject tc thc ae~ion of a gss burner from the ~ront. ~ cable loc~tsd bebind it was undama~ed afte~ 20 ~ tes.
A falli~g apart of the c~s~ion a5 i~ the c2se ~itho~t a su~a~ addi-tion, did ~o~ occ~r due ~o th~ carbo~ ~keleto~-fo~m~g 3u~ar.
E~mple 20 10~5 ~ of a precipi~atio~ silica were suspended ;n 150 ~1 of wa~r.
0.2g o~ pol~eth~lene iml~ie were added to ~his highl~ l;quid suspe~-sio~, followed b~ vigoro~s ~tirring~ The s~s~e~sion -~^~ckened ia~d had a~ o~Low YiS~osi~ o 18 seco~ds.
.. _ . . _ _ . . .... ... .
..... ~ .. . . . , . , . ,, ., , ; ; . ~ . , ., . - , , ~ , r.: ~ :
2:l~19~7 - ~1 -~ele 21 5g o~ be3l~o~e (Eor~ 33:-~ or ~: 129-:E[, t~ademark o~ Ambe::ger ~aol;nwerke, ~mberg, Ger~a~y, or ~entoni~e D~B g) w2re s~spended iQ 2~0 ml of water, accompa~ied by stirri~g with an electrical g~ir-rinæ rod. ~o this highly li~id ~spen~og ~ith a viscosity of 11 seconds ~n ~he DIN c~ (4 ~m~ WOEe added ~.7g of a 20~ polyethy-lene ~mi~e ~ol~on i~ watPr, follow~d by stirring with t~e ~tirri~g rod~ ~he o~t~low time i~ the 4 mm DIN cup was then 14-15 secc~ds anh the spraying and adheslan beh~v~o~r wa~ ~ood. 0~ hea~ the ~pr~yed sJr~ees no ~dhesion problems occurTed ~nd a large 2mo~t of steam wa~ ormed.
~!æa!~
As ~ample 21, b~t ~siD~ 3g o~ beQto~ ~e. The out~low time was 13 seconds a~d the O~p~ay~g behavio~r good, the adhes~on behavio~r ~o cold sur~aces satis~a$tory a~d o~ hot sur~ae~3 goot.
~ZE~ Z~ ~COmp~rison e~ample) ~ike ~ample 21, bnt accom~an~ed b~ ehe addition of 20 ml of 2 mi~ture of 1~ of ~nar O~o~ ;n 100 ml of water. There was only a ht thi~ken~ng ~ction and 8 dea~ a~eous phase separated on ~he bot~om of the cup~ Guar xmm alone does ~ot act a~ a thicke~er i~ the case o~ the pre~e~ lo~ benton~t~ con~ent~aeion~.
... , .. ~
.
Claims (12)
1. Preparation and use of a fire extinguishing and protection agent from thickened water, characterized by the preparation of a thickened suspension of amorphous, synthetic silica in water with a silica weight proportion of at least 1% and preferably 2 to 9%, with adhesive action of surfaces and structures.
2. Preparation and use of a fire extinguishing and fire protection agent from thickened water, characterized by the preparation of a thickened suspension of amorphous, synthetic silica or bentonite in water with a silica or bentonite weight proportion of at least 1%, preferably 2 to 9% and the addition of 0.003 to 1.5, preferably 0.007 to 0.5% by weight, based on the total quantity of the fire extinguishing agent, of polyethylene glycols/polyoxyethylene with molar masses of >700 to <600,000 or derivatives of polyethylene glycol/polyoxyethylene such as polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty acid esters and their mixtures, as well as polyoxyethylene sugar alcohol fatty acid esters with molar masses of 300 or higher, or polyethylene imines as thickening agents.
3. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1/2, characterized by a reinforcement of the thickening and adhesive action of the thickened aqueous suspension of amorphous, synthetic silica by the spraying process with conventional fire extinguishers, or by an intense stirring or mixing process.
4. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 3, character-ized in that it can additionally contain carbon skeleton-forming substances.
5. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1/2 and 4, charact-erized in that it additionally contains extinguishing action-improv-ing substances such as e.g. hydrogen carbonates, borates or ammonium phosphates.
6. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 5, character-ized by the use of the thickened aqueous suspension of amorphous, synthetic silica or bentonite as a fire extinguishing agent using conventional fire extinguishers.
7. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 6, character-ized in that as a result of the adhering action it can be deposited as an extinguishing agent supply of flammable or endangered objects and consequently reduces the risk of fire propagation and extends the extinguishing action of the water by avoiding running.
8. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 7, character-ized by the take-up possibility after the end of the extinguishing process to avoid contamination.
9. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 8, character-ized in that even when the water dries, as a result of the remaining, quantity reduced residues of silica or bentonite adhering to the object, it still exerts a fire propagation-reducing action due to their lack of flammability, whilst as a result of their absorbing action brings about a take-up of harmful fire byproducts.
10. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 9, character-ized in that it can be removed again without damaging the objects involved, e.g. by spraying with water.
11. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to 10, character-ized by its use in stationary fire extinguishing equipment and covers and escape aid coverings.
12. Preparation and use of a fire extinguishing and protection agent from thickened water according to claims 1 to ?, character-ized in that it is applied to the points to be protected in suitable envelopes, e.g. in the form of flexible cushions.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4103388.4 | 1991-02-05 | ||
| DE19914103388 DE4103388A1 (en) | 1991-02-05 | 1991-02-05 | Thickened fire extinguishing water contg. amorphous synthetic silica - with sticking property, pref. thickened with polyethylene glycol or its ether or ester |
| DEP4118888.8 | 1991-06-10 | ||
| DE19914118888 DE4118888A1 (en) | 1991-02-05 | 1991-06-10 | Fire extinguishing and protection agents |
| DEP4134870.2 | 1991-10-23 | ||
| DE19914134870 DE4134870A1 (en) | 1991-10-23 | 1991-10-23 | Fire extinguishing and protection agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2101947A1 true CA2101947A1 (en) | 1992-08-06 |
Family
ID=27202161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002101947A Abandoned CA2101947A1 (en) | 1991-02-05 | 1992-02-04 | Fire extinguishing and protection agent |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0570413B1 (en) |
| AT (1) | ATE133573T1 (en) |
| AU (1) | AU1184392A (en) |
| CA (1) | CA2101947A1 (en) |
| DE (2) | DE4290321D2 (en) |
| WO (1) | WO1992013602A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2899818A1 (en) * | 2006-04-13 | 2007-10-19 | Bio Creation Sa | HIGH WATER CONTENT AQUEOUS SOLUTION FOR FIRE FIGHTING |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0776622A1 (en) * | 1992-06-12 | 1997-06-04 | Gernot LÖHNERT | Usage of thickened water as filling for waterbed mattresses, cushions or the like |
| NL9300668A (en) * | 1993-04-20 | 1994-11-16 | Rudolph Arthur Marinus Kooijma | Liquid extinguishing agent |
| DE4338544C1 (en) * | 1993-11-11 | 1995-06-22 | Walter H Maria Wiemeler | Process for drilling or sawing openings in cavity ceilings or walls |
| DE4343728C2 (en) * | 1993-12-21 | 1997-04-24 | Gernot Dr Loehnert | Process for the production of thickened water and its use |
| IL152486A0 (en) | 2002-10-25 | 2003-05-29 | Meir Eini | Alcohol-free cosmetic and pharmaceutical foam carrier |
| US9668972B2 (en) | 2002-10-25 | 2017-06-06 | Foamix Pharmaceuticals Ltd. | Nonsteroidal immunomodulating kit and composition and uses thereof |
| US9265725B2 (en) | 2002-10-25 | 2016-02-23 | Foamix Pharmaceuticals Ltd. | Dicarboxylic acid foamable vehicle and pharmaceutical compositions thereof |
| US7700076B2 (en) | 2002-10-25 | 2010-04-20 | Foamix, Ltd. | Penetrating pharmaceutical foam |
| US20080138296A1 (en) | 2002-10-25 | 2008-06-12 | Foamix Ltd. | Foam prepared from nanoemulsions and uses |
| US7820145B2 (en) | 2003-08-04 | 2010-10-26 | Foamix Ltd. | Oleaginous pharmaceutical and cosmetic foam |
| US10117812B2 (en) | 2002-10-25 | 2018-11-06 | Foamix Pharmaceuticals Ltd. | Foamable composition combining a polar solvent and a hydrophobic carrier |
| US9211259B2 (en) | 2002-11-29 | 2015-12-15 | Foamix Pharmaceuticals Ltd. | Antibiotic kit and composition and uses thereof |
| NZ540166A (en) | 2002-10-25 | 2007-06-29 | Foamix Ltd | Cosmetic and pharmaceutical foam |
| US7704518B2 (en) | 2003-08-04 | 2010-04-27 | Foamix, Ltd. | Foamable vehicle and pharmaceutical compositions thereof |
| EP1670435A2 (en) * | 2003-08-04 | 2006-06-21 | Foamix Ltd. | Foam carrier containing amphiphilic copolymeric gelling agent |
| US8795693B2 (en) | 2003-08-04 | 2014-08-05 | Foamix Ltd. | Compositions with modulating agents |
| ES2264896B1 (en) * | 2005-07-08 | 2008-02-01 | Empresa De Gestion Medioambiental, S.A. | FLAME RETARDATING COMPOSITION. |
| US20080260655A1 (en) | 2006-11-14 | 2008-10-23 | Dov Tamarkin | Substantially non-aqueous foamable petrolatum based pharmaceutical and cosmetic compositions and their uses |
| US8636982B2 (en) | 2007-08-07 | 2014-01-28 | Foamix Ltd. | Wax foamable vehicle and pharmaceutical compositions thereof |
| US9439857B2 (en) | 2007-11-30 | 2016-09-13 | Foamix Pharmaceuticals Ltd. | Foam containing benzoyl peroxide |
| WO2009090495A2 (en) | 2007-12-07 | 2009-07-23 | Foamix Ltd. | Oil and liquid silicone foamable carriers and formulations |
| US20120087872A1 (en) | 2009-04-28 | 2012-04-12 | Foamix Ltd. | Foamable Vehicles and Pharmaceutical Compositions Comprising Aprotic Polar Solvents and Uses Thereof |
| WO2011013008A2 (en) | 2009-07-29 | 2011-02-03 | Foamix Ltd. | Non surface active agent non polymeric agent hydro-alcoholic foamable compositions, breakable foams and their uses |
| WO2011013009A2 (en) | 2009-07-29 | 2011-02-03 | Foamix Ltd. | Non surfactant hydro-alcoholic foamable compositions, breakable foams and their uses |
| US9849142B2 (en) | 2009-10-02 | 2017-12-26 | Foamix Pharmaceuticals Ltd. | Methods for accelerated return of skin integrity and for the treatment of impetigo |
| EP2482788B1 (en) | 2009-10-02 | 2022-12-14 | Journey Medical Corporation | Topical tetracycline compositions |
| DE102013112063A1 (en) | 2013-11-01 | 2015-05-07 | Viktor Bauf | Fire retardant or fire retardant composition and its use |
| MX2017011630A (en) | 2016-09-08 | 2018-09-25 | Foamix Pharmaceuticals Ltd | Compositions and methods for treating rosacea and acne. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3074883A (en) * | 1961-06-28 | 1963-01-22 | Gen Electric | Fire extinguishing means |
| US3334045A (en) * | 1964-11-27 | 1967-08-01 | Arizona Agrochemical Corp | Fire retardant composition and method |
| GB1349508A (en) * | 1970-02-05 | 1974-04-03 | Ici Ltd | Fire fighting and compositions for use therein |
| US3912647A (en) * | 1973-12-06 | 1975-10-14 | Franklin Z Adell | Invert emulsion fire extinguishing composition and method |
| US4173538A (en) * | 1975-10-08 | 1979-11-06 | Herbline Celestin L | Extinguishing product comprising an uninflammable powder and liquid |
| US3976580A (en) * | 1975-11-07 | 1976-08-24 | Bernard Kaminstein | Gelled fire extinguisher fluid comprising polyacrylamide and bentonite |
| HU186325B (en) * | 1984-08-06 | 1985-07-29 | Mta Termeszettudomanyai Kutato | Method for producing gels of reversible water-absorbing capacity and stabilized structure containing clay mineral |
-
1992
- 1992-02-04 AT AT92903639T patent/ATE133573T1/en not_active IP Right Cessation
- 1992-02-04 CA CA002101947A patent/CA2101947A1/en not_active Abandoned
- 1992-02-04 DE DEDE9200070T patent/DE4290321D2/en not_active Expired - Fee Related
- 1992-02-04 DE DE59205254T patent/DE59205254D1/en not_active Expired - Fee Related
- 1992-02-04 EP EP92903639A patent/EP0570413B1/en not_active Expired - Lifetime
- 1992-02-04 AU AU11843/92A patent/AU1184392A/en not_active Abandoned
- 1992-02-04 WO PCT/DE1992/000070 patent/WO1992013602A1/en active IP Right Grant
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2899818A1 (en) * | 2006-04-13 | 2007-10-19 | Bio Creation Sa | HIGH WATER CONTENT AQUEOUS SOLUTION FOR FIRE FIGHTING |
| WO2007122342A2 (en) * | 2006-04-13 | 2007-11-01 | Bio Creation | Composition for fire fighting and formulations of said composition |
| WO2007122342A3 (en) * | 2006-04-13 | 2008-09-12 | Bio Creation | Composition for fire fighting and formulations of said composition |
| JP2009533118A (en) * | 2006-04-13 | 2009-09-17 | ビオ、クレアスィオン | Fire fighting composition and preparation of the composition |
| US7922928B2 (en) | 2006-04-13 | 2011-04-12 | Lanciaux Marc | Composition for fire fighting and formulations of said composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992013602A1 (en) | 1992-08-20 |
| EP0570413A1 (en) | 1993-11-24 |
| EP0570413B1 (en) | 1996-01-31 |
| DE59205254D1 (en) | 1996-03-14 |
| DE4290321D2 (en) | 1994-04-28 |
| AU1184392A (en) | 1992-09-07 |
| ATE133573T1 (en) | 1996-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |