CA2091491A1 - Geopolymer-modified, gypsum-based construction material - Google Patents
Geopolymer-modified, gypsum-based construction materialInfo
- Publication number
- CA2091491A1 CA2091491A1 CA 2091491 CA2091491A CA2091491A1 CA 2091491 A1 CA2091491 A1 CA 2091491A1 CA 2091491 CA2091491 CA 2091491 CA 2091491 A CA2091491 A CA 2091491A CA 2091491 A1 CA2091491 A1 CA 2091491A1
- Authority
- CA
- Canada
- Prior art keywords
- gypsum wallboard
- geopolymer
- gypsum
- wallboard material
- gyp
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/28—Mixtures thereof with other inorganic cementitious materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/003—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hybrid binders other than those of the polycarboxylate type
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
ABSTRACT
Geopolymer-modified gypsum construction materials.
Compositions derived from combining geopolymer adhesives with conventional gypsum wallboard slurry formulations produce an interpenetrating network (IPN) which cures by loss of process water to a refractory solid having improved fire and water resistance. Geopolymer adhesive starting compositions include soluble and insoluble silicates, buffers and salts, and a chemical setting agent in aqueous suspension.
Geopolymer-modified gypsum construction materials.
Compositions derived from combining geopolymer adhesives with conventional gypsum wallboard slurry formulations produce an interpenetrating network (IPN) which cures by loss of process water to a refractory solid having improved fire and water resistance. Geopolymer adhesive starting compositions include soluble and insoluble silicates, buffers and salts, and a chemical setting agent in aqueous suspension.
Description
2~914~1 ~he pre~ent inventlon r~lates generally to ~yp~um w~llbo~rd con4~ruction ~aterial, and more paxtlculaxly to the m~d~lc~tion o~ eu~h m~terl~l~ hy th~ ~dition of silia~-b~sed gaop~lymer adhezi~e~ to produce ~ompo~ite~ :
whi~h exhibit ~proved ~r~ performAnc~ ~ water r~ Sanc~, ~nd ~truatural prop~rt3 G~peum wall~oard ~5 a widely u~ed cen~tru~tion m~texi~l becAuse of it3 low co~t and fire reQi3t~nce. Fire : ~ :~
resl~tance capability io generally proport$onal to ~he th~cknbs~ o~ the gyp3um smploy~d i~ a firo re~i~ting structuro~ For example, ~ simpl~ st~uaturo approv-d ~or ~ ~ire endurance per~od of one hour u3e~ a 5/8" thick ~
sla~ of ~ype X gyp~um w~llboard on either side of a 3-5/ ~:;
8`' metal ~tud with ~n Alr flllad cavity for ~ non-lo~-bearin~ w~ ombly. Othor d~olgn~ provide fir~
r~lot~noe fo~ perio~ of up to two hou~o.
Gyp~um l~ ~ natuxAlly occurring form o~ the dl-hydrate o~ aal~ium sulfat~. ~his ma~erl~l can ~e readlly tran~crm~d ~o its ~tucco ~orm, the hemi-hydrate of calaium oul~ate, by ono o~ ~everal calcin~tion procoe~eo. Gyp3um provide~ fire prot~ction through two pximary mechasli~m~s the non-aombustible nat~r~ o~ :
inorg~nic compounds; ~nd th~ endothermic, en~rgy-P~5 d Z~ZJ 6 b9 ~3W::l '8 NOS NII'1al~a ~:80 6, Wl^l -' 2~91~91 a~orblng CApACity of th~ dihydrate which pr~duee~ s~e~
wh~n expo~ed to ~n~n~ heat. ~n equ~tlon or~, gyp~um S ~ Pla~ter o¢ Pari~ + stoam - ~nergy, or CaSO~ (2~20) ~ ca8~4 (~5~2) ~ 1.5~0 - 4100 aal/~ole.
A wall whieh is to endure ~ire ~or a p~ried ~ at laaat one hour mu~t be able to with~And t~mper~tur~g w~ n oxoes~ o~ 1500~. ~hl~ ~-emporaturo i0 aon~iderably in exae~ o~ the ignltlon temper~tur~ of mo~t organic m~teriala ~a~ou~ 450-aO0F). ~hus, ~ ~ire-ra~lstant wall mu~t m~lntain the t~mp~ra~ure of the unexpo3ed fa~
a~ the w~ t a moderat ely low temperature in order to 15 prevent the spr~ad o~ th~ f ire . A further con~lde~ation or ~n ~captable ~i~e-re3~stant wall i5 the lnta~rity o~ the wall a~embly ag~inst penetration by d water ~traa~ ~rom a ~lre h w e at th~ terminatlon o the flre expo~ura per~od. Ma~onry wall~ achi~o th~se condition~
20 o.~ a result o~ th~ high ~tructural~thermal ma~ and large haat aapa~ity inh~rent in the dense material~
uti~i~ed. ~ishtweisht wall a~sem~lie~, by con~rast, requira ~ood th~rm~l in~ulatlon ln li~u o~ lar~ th~r~Al ma~s . ~he utlll~atlon o~ the he~t of dehydration o~
25 gyp5um can ~rovide an e~fective aooli~g meahanism for a ~lre-roai~tant wall. ~wover, a~ thi~ water of hydration, which bind~ the gyp~um ~aterial, is ~onY~t~d ~f9 -~ 2~Z~ 6 b9 ~3W~ ~ NOS NI~1altla P :80 6, W~
- 2 ~
whi~h exhibit ~proved ~r~ performAnc~ ~ water r~ Sanc~, ~nd ~truatural prop~rt3 G~peum wall~oard ~5 a widely u~ed cen~tru~tion m~texi~l becAuse of it3 low co~t and fire reQi3t~nce. Fire : ~ :~
resl~tance capability io generally proport$onal to ~he th~cknbs~ o~ the gyp3um smploy~d i~ a firo re~i~ting structuro~ For example, ~ simpl~ st~uaturo approv-d ~or ~ ~ire endurance per~od of one hour u3e~ a 5/8" thick ~
sla~ of ~ype X gyp~um w~llboard on either side of a 3-5/ ~:;
8`' metal ~tud with ~n Alr flllad cavity for ~ non-lo~-bearin~ w~ ombly. Othor d~olgn~ provide fir~
r~lot~noe fo~ perio~ of up to two hou~o.
Gyp~um l~ ~ natuxAlly occurring form o~ the dl-hydrate o~ aal~ium sulfat~. ~his ma~erl~l can ~e readlly tran~crm~d ~o its ~tucco ~orm, the hemi-hydrate of calaium oul~ate, by ono o~ ~everal calcin~tion procoe~eo. Gyp3um provide~ fire prot~ction through two pximary mechasli~m~s the non-aombustible nat~r~ o~ :
inorg~nic compounds; ~nd th~ endothermic, en~rgy-P~5 d Z~ZJ 6 b9 ~3W::l '8 NOS NII'1al~a ~:80 6, Wl^l -' 2~91~91 a~orblng CApACity of th~ dihydrate which pr~duee~ s~e~
wh~n expo~ed to ~n~n~ heat. ~n equ~tlon or~, gyp~um S ~ Pla~ter o¢ Pari~ + stoam - ~nergy, or CaSO~ (2~20) ~ ca8~4 (~5~2) ~ 1.5~0 - 4100 aal/~ole.
A wall whieh is to endure ~ire ~or a p~ried ~ at laaat one hour mu~t be able to with~And t~mper~tur~g w~ n oxoes~ o~ 1500~. ~hl~ ~-emporaturo i0 aon~iderably in exae~ o~ the ignltlon temper~tur~ of mo~t organic m~teriala ~a~ou~ 450-aO0F). ~hus, ~ ~ire-ra~lstant wall mu~t m~lntain the t~mp~ra~ure of the unexpo3ed fa~
a~ the w~ t a moderat ely low temperature in order to 15 prevent the spr~ad o~ th~ f ire . A further con~lde~ation or ~n ~captable ~i~e-re3~stant wall i5 the lnta~rity o~ the wall a~embly ag~inst penetration by d water ~traa~ ~rom a ~lre h w e at th~ terminatlon o the flre expo~ura per~od. Ma~onry wall~ achi~o th~se condition~
20 o.~ a result o~ th~ high ~tructural~thermal ma~ and large haat aapa~ity inh~rent in the dense material~
uti~i~ed. ~ishtweisht wall a~sem~lie~, by con~rast, requira ~ood th~rm~l in~ulatlon ln li~u o~ lar~ th~r~Al ma~s . ~he utlll~atlon o~ the he~t of dehydration o~
25 gyp5um can ~rovide an e~fective aooli~g meahanism for a ~lre-roai~tant wall. ~wover, a~ thi~ water of hydration, which bind~ the gyp~um ~aterial, is ~onY~t~d ~f9 -~ 2~Z~ 6 b9 ~3W~ ~ NOS NI~1altla P :80 6, W~
- 2 ~
to ~t~a~, th~ gyp~ recal~ined ~nto a f~ h~
hydra~o powter~ or ~tucco~ leaYin~ a wa~.l componen~ that 5 is d~3void of stru~tur~l integrity, lackin~ dim~3n~ion~1 ~tabllity~ and without 3t~0ngth after ~lre~ exp~3ure. :~:
Moraover~ th~ recalcinod gyp~u~ material 1~ e~ily ~ :
waahed AWa~ with water ~OSA a fire ho3~. At a $1ini~
the wall i~ easily crumbled ~y the Rction of water from flro hos~a ~cause of ~hrir~klng and b~ndinq o~ the stud~ -as well 20 from th~ shrink~ng o~ th~ qypwm it3~1~ which p~odu~es oracks theroin. ~ :
StructU~Bl rigidity o~ gyp8UJA wallboard, ~hioh 1 lS proportional to ths mom~nt of inerti~ o~ ~ho p~por fAcing ~h~et~ about the bending axis, d~riv~ ~ro~n the b~nd of tho paper to the c~o~e. ~rh~ bond i~ affected by the dag~e o~ ~aturation o~ tho p~per whic~h ~l~o promot~ ~ehydr~tion and cry~tallln~ growth of the 20 gyp~um Lnto the paper. In ~ddit~on, the compxoe~i~e str~nslth o~ the ~yp~um core i,9 proport~onal to the den~Lty, tha type o~ ory3talliBation~ and tho degxeo of ~ehydratlon. Of the n~turally occurring ~orm~ of gyp~ th~ are common. Acicul~r or n~edle-like 2S satin~par and plate-llk~ ~elenltQ do not havo ad~guate ~tru~tural integxity to bo of ~nteres~ in the constx~lc~ion trade8~ and phygical condition~ whiCh t~ 'J 2~Z~ 5 b9 ~3W~ ~ NOS NIMal~a b:~0 ~6, W~
:-` 2~9~9~
promote the growth o~ these form~ prev~n~ the formatio~ :
o~ structural 9yp51~ iYe qypBlam, ~r alaba~er, has S random throe-d~en~ional c~ystalline orientat~on, an~ ~:
whL}e not hlghly ~oluble in water, it ~8 hy~xo~co~io and will so~en when w~t. During th~s condition, lt lo~es most of it~ strength and in A wa11board ~t~ucture, ~he gypsum~p~per ory~tal}lne bon~ l~ ea~ily destroyed or ~0 damag~d. If proporly dried, the core 3tren~th ~$11 return.
Ca~o mu~t b~ exerci~ed in the ~election of ~dditives for syp~um wAllbo~r~, slnc~ a poor cho~co of 2dditive~ say lS ~Au~e impropcr recrystalli~ation tdevelopment o~ an int~rpenqtratlng network through r~ndom cry~talllne growth), with a resul~Lng 1~s of ~trength both in the coro ~nd in the pap~r f~clns shee~ bond. In ~ddition, th~ ~re~en~ of 401uble salt~ ~nd other impurit~e~
~ ct3 ths gyp~um/paper bond ant the cere ~tr~ngth d¢trimentally. ~inally~ the settlng tl~e~ whi~h i~
dlrectly related to the ~ate o~ rehydr~tion and release of heat, ~u~t be maint~in~d ~i~hin 4trict liml~ to meet operational crtteria of ~ wall boa~d man~acturlng ~5 ~roa~3 ~pecificatlon ~h~t is, the ~ix ~t xetain a worXin~ co~ity whlle in thq mlxer and durlng the w~ttln~ of the papor ~a~ing ~heot~, must be plastl~ but ~,'Z-d I~ZIZI~J 6 ~9 ~3W~ ~ NOS NIMa~a ~ ;8E1 ~6, `WW ~1 '` 20~1~9~ :
- 5 - ~
~' ~
h~ld its form while pa~ing through the forming rolls and 3moothlng baxs, and mu~t ~ure to mod~rat~ handling 3tren$th suffi~i~nt ~or cutt~ng and tran3port to the dryer w~thin the length o~ a productlon l~ne which i9 typl~ally 4-~ min for a 1000 ~t lln~ and a ~o~rd movement rate of 200-~S0 ft/mi~
~otard~r~ are ~ed to prevent initial setting during tho flr~t p~a~e ~nd acc~l~rator~ aro used to produce ~i~Al set with~n the pxoper tlme p~riod. D~fferent compound~
~ ct the in~tial s~t ~nd xehydratlon oycle and the chemi~try be~o~e~ oomplox and highly proprietary. The lS ~rimary accelerator i~ the add~tion o~ freshly ground ma~ive gypsum as a seed cry~tal. Without r~tardatlon, typically by us~ng w~t~r-soluble organi~ aald~ or ~ase~, tho nucl~tion will proaeed to rapid initial ~et, the~e~y prevonting propdr w-tt~ng and ~orming.
AdditlonAl a~celesator~ ~u~h a3 pota~h, ~or example, aro : :
employed to enhanco tho rohydration pha~e to produce "Vioat SetH. ~hat iBI the point where the ~tre~gth measured by a Vica~ hardness ~e~ter i5 ad~quate for ~uttLn~ and dryln~, at which tLme the rehydration ~xoth~rm ha~ n~axly reached ~ompl~tion and the tempe~tu~e o~ th2 materl~l rem~ins approx$matsly con~tant .
~~6-d ~Z~ZF~ 6 bg ~3~3 ~ NOS NIMa~s P~:8~ 6, Wl~
2 ~
N~t~ral ~a~ e gyp~u~ hR~ a d~n~ity o~ ~bout 2.35 g~cm3 (147 lb~t3~ whlch i8 approxlma~ely thre2 timea the den~ity of typical fire-resistant gyp~u~ wallboard t47 lb/ft3~. Recon~titution of ~a~lve gyp~u~ di-hy~r~te at atmosph~ria pre~ure w~ll net produca th~ ~igh d~n~ity of the natur~l gypsum becausa of the requirem~nt o exce~ water to gen~rate a workabl~ slur~y mlxture. The cured ~en~lty o~ Plast~ o~ ~ar~ r~nges ~r~m a high o 2bout 75 lb~t3 with a ~ater;~tuooo w~ welght r~tLo of ~ :
0.8 to ~ low of 36 lb~ft3 with a ~oxr~sponding r~tlo of 1.7. Compre~o~ve strength ~119 ~ro~ 2000 p9i to 170 p~l, ra~pecti~oly. ~he exact formulA sp~olflcation o~
1~ 1.5 moles o~ water add~d to one ~ols o~ calcium sul~ate h-ml-hydr~te to produce the ~s~Lv~ gyp~um corro~ponds to ~ w~ter~t~cco ratlo of 0.186. Genar~lly, the amount o~ a~llable water dir~otly ~ot8rm1ne4 the ~n~1 cured snrP~ en~llty.
A~cordingly, an ob~oct o~ the pre~ent invention i~ to provlda a gyp~um-~ased oonet~uctLon ~aterial~ having improved fire and water resistance and~or ~ method of produçing sama or which at leaot will prov~de the pu~
as wi~h a u~e~ul choic~.
Addltion~l objeot3, advantage~ aDd novel f~ture~ o~ th~
~nvention will ~ ~et forth i~ p~rt in th~ deacript~on 0~'d ZIZJ 6 b9 ~3W3 '8 NOS NIMal~a SP:0 ~6, Wl --` 2091~
whiah follows~ and 1Y~ p~rt will beeom~ app~rent to those ~kill~d irl th~ ~xt upon exa~lnation o~ tho ~ollowing or :
5 mAy b~ learned by pr~otice of ~ha inventlon. ~he oh~e¢ts and advantage~ of tho ~.nvent~o~ may be r~ali~ed a~d attain~d ~y means o~ the lnstru~n~allt~ and co~bination~ parti~ularly po~n~d out ln the appended clai~, ,~ , Ac~ordlDg ~o one ~peat o~ the pre~nt invelltion the~e i~ thu~ provided fl 9}'p~Um wallboard mate~ial having l~prov~d ire ~nd water ro~istance ~?roduced ~rom com~lning a sel~-hardening ~ixtur~ c~mpri~ing 15 geopolynser adhe~iv~ wlth a gyp~m wall~oQrd 91u~xy, wherein said geopoly~er adhe6ive ocmprlses a Bolu~le cllkall metal ~llicate ~olution, a chemioal ~etting agent and a th~ckening a3ent.
,... ..
Aocordlng to a furth~r ~pe~t of tho pr~e~t invention thors ~9 provited a method fo~ p~oduclng a gyp~
wallboAxd m~te~lal having impxoved fi~e and water resistance, qaid xethod comprising the steps o~
a) combin~ng a ~elf-har~e~in~ mixturo aompri~ng qyp~um wallbo~lrd slurry with a ge~polymer adhe~ive, said goopolymer adhe~ive comprising a ~olul~le al)cali motal oilicate ~olut~on, : ''.
EZ~ZL 6 b9 03W~ ~ NOS NIMa~tla ~ 80 6, ;~ W 1~ -~ 2091~91 thickening ~ent, and a Ghem~cal ~tin~ a~ont;
and b) p~r~l~ting the ~ixtur~ r~sulting thersfrom to hard~n.
~he ac~ompanying drawing~ which are incorporated in and ~or~ a p2rt ~f the ~p~c~f~catio~, lllu~trate two 3mbodimen~s o~ tho pr~nt inv~ntion, and together wi~h the de~criptlon, serve to explaln the p~nciples of the ~nventlon. In the drawL~g~:
Piaure lt Curve 1 illustrat~ a typical setting-temperature versuh tim~ rehydratlon ~or conventi4nal gypsum wallboArd formulAtion~
Curv~ 2 illu~trates a ~imllar rehydr~tion profile to thAt shown i~ Curve 1 hereo~ for a compo~ltion includlng the gyp~um wallbo~rd ~ormulation th~reof with Addet geopolym~x adhe~ive a~Gordlng to the teachings o~ tbe preso~t inventlon (the ~ormulAtion doe~ not contain ~ocele~tor, retard~r, or flya3h materLals];
Curve 3 illu~trAtea a sia~lar rshydratlon profile to that ~hown in Curve 2 hereof, oxcept t~at flyash hae ~en added to the ~or~ul~tion.
b/ZI d 21Z~ 6 b9 ~3~ NOS NIMal~a Sb:80 6, ;~ W
'- 2~ gl Figure 2: Illu~tr~t~ tho comp~es~i~e yiold of ~a~-exi~l~
produ~ed ac~ord~ng ~v the te~ching~ o~ the p~e~ent inv2ntion ;15 a function of th~ den~ity ther~o , Fi~ure_3: ~llu~trate~ ~ comp~ri~on fir~ te~t ~etween conventional Snrp8t~m wallboArd an~ wallboard prsduced acc:ording to ths te~ching3 of the p~e6ent invention.
Brief ly, the pre~en$ lnvention includes compo~itions :
th~t resul~ ~!rom aombinin~ geopoly3ler adhesi~,re~ wlth gyp~u~ ~lurry ~ormulat~on~ to produce ~ntarpe~lotrating ~ .
n~tt~rork~ ~IPNs) whlch cure to form refrac~ory ~clids by lo~ o~ process ~A~-er. Gecpolymer adhesive component~
inclu~e: ~oluble and in~oluble silioate~; buffe~s~ ~alts in ao"ueou~ 2ua pe,n~ion ~ and cho~Lcal ~tting agent3 . The CU~iDg oyclo o~ the g60polymer m~tF~ri~1 begins with th~a ~ormation o~ a ~ompl~c~tod liqu~d or g~l o cation~
~c42+~ zn2+, ~to) ar~d anion ~mplexea. ~ho ~nionl~
constituent~ thon poly~ori3e, forming ah6in~ that are a~o~s-l~nkQd by the o~tion~. ~he ~inal oom~o~ition of ;
th~ qeopolymer IPN (in the ab~ence of the gyp~m-b~sed mat0rial~) i8 a polymexl~ed ~ilica matrix which mdy 2S incorporate di~per~ed-phasQ particle8, ~Ibre~, fillers and extend~ra. In Addition, slnce there i~ no chemic~l or st~u~tur~l dep~nd~nae on wat~r in the re~ult~ng d ~Z~ZF~ 6 b9 ~lW~ '8 NOS NIMa~t~8 9b ~ 6, Wl`l ''`'~ t; '.. ,., .. , .. , ; ," ", ~ , "
--~ 2~91~1 sl1ic~ matrix, when ~n~orporated ~nto ~yp~um-ba~ed construct~on materlal~ accordlng to the t~chin~s o~ ths preoo~t ~ention, the refra~tory IPN provides ths rema~nl~g ~tructure to ~yp~u~-based wallbo~rd ~~er tuh composttion~ ~re expo~ed to ~ire.
According to present understanding o~ the inventlon, the ~0 Rddltion o~ geopolymer ~dhe~ive9 ~o ~yp8~m ~lurrie3 provlde~ the followi~q:
1. Crosa-lln~n~ of the gyp~u~ through geopolym~r IPN
stru~tura~; that i9, a retioul~ted co--~ructur~, ~Arallel to the xAndom cxyatallis4tion o tho gyp~
2. ~he ~oopolymer ~PN i~ no~ des~royed upon . re~alcining o~ the gypsum, and thc ~tructural ao integrity o~ t~e çompos~te a~tor fire expo~ure re~ist~ cxumbling to ~ dsgr~e whlch i~
proportlcnal t~ the amount of geopolyme~ adhe3ivet e~ployedt 3, ~he in~olu~le nature d th~ geopolymer IPN
i~prove~ the performance of ~he composit~ matrix when e~pooed to w~ter, minimlt~ng ~to~taning etCJ
and ~.~bl'd E21Z~ 6 b9 ~3;~ 1`105 NIMa3t~1 gb:i~1 6, ~:ltll`l 11 209~
hydra~o powter~ or ~tucco~ leaYin~ a wa~.l componen~ that 5 is d~3void of stru~tur~l integrity, lackin~ dim~3n~ion~1 ~tabllity~ and without 3t~0ngth after ~lre~ exp~3ure. :~:
Moraover~ th~ recalcinod gyp~u~ material 1~ e~ily ~ :
waahed AWa~ with water ~OSA a fire ho3~. At a $1ini~
the wall i~ easily crumbled ~y the Rction of water from flro hos~a ~cause of ~hrir~klng and b~ndinq o~ the stud~ -as well 20 from th~ shrink~ng o~ th~ qypwm it3~1~ which p~odu~es oracks theroin. ~ :
StructU~Bl rigidity o~ gyp8UJA wallboard, ~hioh 1 lS proportional to ths mom~nt of inerti~ o~ ~ho p~por fAcing ~h~et~ about the bending axis, d~riv~ ~ro~n the b~nd of tho paper to the c~o~e. ~rh~ bond i~ affected by the dag~e o~ ~aturation o~ tho p~per whic~h ~l~o promot~ ~ehydr~tion and cry~tallln~ growth of the 20 gyp~um Lnto the paper. In ~ddit~on, the compxoe~i~e str~nslth o~ the ~yp~um core i,9 proport~onal to the den~Lty, tha type o~ ory3talliBation~ and tho degxeo of ~ehydratlon. Of the n~turally occurring ~orm~ of gyp~ th~ are common. Acicul~r or n~edle-like 2S satin~par and plate-llk~ ~elenltQ do not havo ad~guate ~tru~tural integxity to bo of ~nteres~ in the constx~lc~ion trade8~ and phygical condition~ whiCh t~ 'J 2~Z~ 5 b9 ~3W~ ~ NOS NIMal~a b:~0 ~6, W~
:-` 2~9~9~
promote the growth o~ these form~ prev~n~ the formatio~ :
o~ structural 9yp51~ iYe qypBlam, ~r alaba~er, has S random throe-d~en~ional c~ystalline orientat~on, an~ ~:
whL}e not hlghly ~oluble in water, it ~8 hy~xo~co~io and will so~en when w~t. During th~s condition, lt lo~es most of it~ strength and in A wa11board ~t~ucture, ~he gypsum~p~per ory~tal}lne bon~ l~ ea~ily destroyed or ~0 damag~d. If proporly dried, the core 3tren~th ~$11 return.
Ca~o mu~t b~ exerci~ed in the ~election of ~dditives for syp~um wAllbo~r~, slnc~ a poor cho~co of 2dditive~ say lS ~Au~e impropcr recrystalli~ation tdevelopment o~ an int~rpenqtratlng network through r~ndom cry~talllne growth), with a resul~Lng 1~s of ~trength both in the coro ~nd in the pap~r f~clns shee~ bond. In ~ddition, th~ ~re~en~ of 401uble salt~ ~nd other impurit~e~
~ ct3 ths gyp~um/paper bond ant the cere ~tr~ngth d¢trimentally. ~inally~ the settlng tl~e~ whi~h i~
dlrectly related to the ~ate o~ rehydr~tion and release of heat, ~u~t be maint~in~d ~i~hin 4trict liml~ to meet operational crtteria of ~ wall boa~d man~acturlng ~5 ~roa~3 ~pecificatlon ~h~t is, the ~ix ~t xetain a worXin~ co~ity whlle in thq mlxer and durlng the w~ttln~ of the papor ~a~ing ~heot~, must be plastl~ but ~,'Z-d I~ZIZI~J 6 ~9 ~3W~ ~ NOS NIMa~a ~ ;8E1 ~6, `WW ~1 '` 20~1~9~ :
- 5 - ~
~' ~
h~ld its form while pa~ing through the forming rolls and 3moothlng baxs, and mu~t ~ure to mod~rat~ handling 3tren$th suffi~i~nt ~or cutt~ng and tran3port to the dryer w~thin the length o~ a productlon l~ne which i9 typl~ally 4-~ min for a 1000 ~t lln~ and a ~o~rd movement rate of 200-~S0 ft/mi~
~otard~r~ are ~ed to prevent initial setting during tho flr~t p~a~e ~nd acc~l~rator~ aro used to produce ~i~Al set with~n the pxoper tlme p~riod. D~fferent compound~
~ ct the in~tial s~t ~nd xehydratlon oycle and the chemi~try be~o~e~ oomplox and highly proprietary. The lS ~rimary accelerator i~ the add~tion o~ freshly ground ma~ive gypsum as a seed cry~tal. Without r~tardatlon, typically by us~ng w~t~r-soluble organi~ aald~ or ~ase~, tho nucl~tion will proaeed to rapid initial ~et, the~e~y prevonting propdr w-tt~ng and ~orming.
AdditlonAl a~celesator~ ~u~h a3 pota~h, ~or example, aro : :
employed to enhanco tho rohydration pha~e to produce "Vioat SetH. ~hat iBI the point where the ~tre~gth measured by a Vica~ hardness ~e~ter i5 ad~quate for ~uttLn~ and dryln~, at which tLme the rehydration ~xoth~rm ha~ n~axly reached ~ompl~tion and the tempe~tu~e o~ th2 materl~l rem~ins approx$matsly con~tant .
~~6-d ~Z~ZF~ 6 bg ~3~3 ~ NOS NIMa~s P~:8~ 6, Wl~
2 ~
N~t~ral ~a~ e gyp~u~ hR~ a d~n~ity o~ ~bout 2.35 g~cm3 (147 lb~t3~ whlch i8 approxlma~ely thre2 timea the den~ity of typical fire-resistant gyp~u~ wallboard t47 lb/ft3~. Recon~titution of ~a~lve gyp~u~ di-hy~r~te at atmosph~ria pre~ure w~ll net produca th~ ~igh d~n~ity of the natur~l gypsum becausa of the requirem~nt o exce~ water to gen~rate a workabl~ slur~y mlxture. The cured ~en~lty o~ Plast~ o~ ~ar~ r~nges ~r~m a high o 2bout 75 lb~t3 with a ~ater;~tuooo w~ welght r~tLo of ~ :
0.8 to ~ low of 36 lb~ft3 with a ~oxr~sponding r~tlo of 1.7. Compre~o~ve strength ~119 ~ro~ 2000 p9i to 170 p~l, ra~pecti~oly. ~he exact formulA sp~olflcation o~
1~ 1.5 moles o~ water add~d to one ~ols o~ calcium sul~ate h-ml-hydr~te to produce the ~s~Lv~ gyp~um corro~ponds to ~ w~ter~t~cco ratlo of 0.186. Genar~lly, the amount o~ a~llable water dir~otly ~ot8rm1ne4 the ~n~1 cured snrP~ en~llty.
A~cordingly, an ob~oct o~ the pre~ent invention i~ to provlda a gyp~um-~ased oonet~uctLon ~aterial~ having improved fire and water resistance and~or ~ method of produçing sama or which at leaot will prov~de the pu~
as wi~h a u~e~ul choic~.
Addltion~l objeot3, advantage~ aDd novel f~ture~ o~ th~
~nvention will ~ ~et forth i~ p~rt in th~ deacript~on 0~'d ZIZJ 6 b9 ~3W3 '8 NOS NIMal~a SP:0 ~6, Wl --` 2091~
whiah follows~ and 1Y~ p~rt will beeom~ app~rent to those ~kill~d irl th~ ~xt upon exa~lnation o~ tho ~ollowing or :
5 mAy b~ learned by pr~otice of ~ha inventlon. ~he oh~e¢ts and advantage~ of tho ~.nvent~o~ may be r~ali~ed a~d attain~d ~y means o~ the lnstru~n~allt~ and co~bination~ parti~ularly po~n~d out ln the appended clai~, ,~ , Ac~ordlDg ~o one ~peat o~ the pre~nt invelltion the~e i~ thu~ provided fl 9}'p~Um wallboard mate~ial having l~prov~d ire ~nd water ro~istance ~?roduced ~rom com~lning a sel~-hardening ~ixtur~ c~mpri~ing 15 geopolynser adhe~iv~ wlth a gyp~m wall~oQrd 91u~xy, wherein said geopoly~er adhe6ive ocmprlses a Bolu~le cllkall metal ~llicate ~olution, a chemioal ~etting agent and a th~ckening a3ent.
,... ..
Aocordlng to a furth~r ~pe~t of tho pr~e~t invention thors ~9 provited a method fo~ p~oduclng a gyp~
wallboAxd m~te~lal having impxoved fi~e and water resistance, qaid xethod comprising the steps o~
a) combin~ng a ~elf-har~e~in~ mixturo aompri~ng qyp~um wallbo~lrd slurry with a ge~polymer adhe~ive, said goopolymer adhe~ive comprising a ~olul~le al)cali motal oilicate ~olut~on, : ''.
EZ~ZL 6 b9 03W~ ~ NOS NIMa~tla ~ 80 6, ;~ W 1~ -~ 2091~91 thickening ~ent, and a Ghem~cal ~tin~ a~ont;
and b) p~r~l~ting the ~ixtur~ r~sulting thersfrom to hard~n.
~he ac~ompanying drawing~ which are incorporated in and ~or~ a p2rt ~f the ~p~c~f~catio~, lllu~trate two 3mbodimen~s o~ tho pr~nt inv~ntion, and together wi~h the de~criptlon, serve to explaln the p~nciples of the ~nventlon. In the drawL~g~:
Piaure lt Curve 1 illustrat~ a typical setting-temperature versuh tim~ rehydratlon ~or conventi4nal gypsum wallboArd formulAtion~
Curv~ 2 illu~trates a ~imllar rehydr~tion profile to thAt shown i~ Curve 1 hereo~ for a compo~ltion includlng the gyp~um wallbo~rd ~ormulation th~reof with Addet geopolym~x adhe~ive a~Gordlng to the teachings o~ tbe preso~t inventlon (the ~ormulAtion doe~ not contain ~ocele~tor, retard~r, or flya3h materLals];
Curve 3 illu~trAtea a sia~lar rshydratlon profile to that ~hown in Curve 2 hereof, oxcept t~at flyash hae ~en added to the ~or~ul~tion.
b/ZI d 21Z~ 6 b9 ~3~ NOS NIMal~a Sb:80 6, ;~ W
'- 2~ gl Figure 2: Illu~tr~t~ tho comp~es~i~e yiold of ~a~-exi~l~
produ~ed ac~ord~ng ~v the te~ching~ o~ the p~e~ent inv2ntion ;15 a function of th~ den~ity ther~o , Fi~ure_3: ~llu~trate~ ~ comp~ri~on fir~ te~t ~etween conventional Snrp8t~m wallboArd an~ wallboard prsduced acc:ording to ths te~ching3 of the p~e6ent invention.
Brief ly, the pre~en$ lnvention includes compo~itions :
th~t resul~ ~!rom aombinin~ geopoly3ler adhesi~,re~ wlth gyp~u~ ~lurry ~ormulat~on~ to produce ~ntarpe~lotrating ~ .
n~tt~rork~ ~IPNs) whlch cure to form refrac~ory ~clids by lo~ o~ process ~A~-er. Gecpolymer adhesive component~
inclu~e: ~oluble and in~oluble silioate~; buffe~s~ ~alts in ao"ueou~ 2ua pe,n~ion ~ and cho~Lcal ~tting agent3 . The CU~iDg oyclo o~ the g60polymer m~tF~ri~1 begins with th~a ~ormation o~ a ~ompl~c~tod liqu~d or g~l o cation~
~c42+~ zn2+, ~to) ar~d anion ~mplexea. ~ho ~nionl~
constituent~ thon poly~ori3e, forming ah6in~ that are a~o~s-l~nkQd by the o~tion~. ~he ~inal oom~o~ition of ;
th~ qeopolymer IPN (in the ab~ence of the gyp~m-b~sed mat0rial~) i8 a polymexl~ed ~ilica matrix which mdy 2S incorporate di~per~ed-phasQ particle8, ~Ibre~, fillers and extend~ra. In Addition, slnce there i~ no chemic~l or st~u~tur~l dep~nd~nae on wat~r in the re~ult~ng d ~Z~ZF~ 6 b9 ~lW~ '8 NOS NIMa~t~8 9b ~ 6, Wl`l ''`'~ t; '.. ,., .. , .. , ; ," ", ~ , "
--~ 2~91~1 sl1ic~ matrix, when ~n~orporated ~nto ~yp~um-ba~ed construct~on materlal~ accordlng to the t~chin~s o~ ths preoo~t ~ention, the refra~tory IPN provides ths rema~nl~g ~tructure to ~yp~u~-based wallbo~rd ~~er tuh composttion~ ~re expo~ed to ~ire.
According to present understanding o~ the inventlon, the ~0 Rddltion o~ geopolymer ~dhe~ive9 ~o ~yp8~m ~lurrie3 provlde~ the followi~q:
1. Crosa-lln~n~ of the gyp~u~ through geopolym~r IPN
stru~tura~; that i9, a retioul~ted co--~ructur~, ~Arallel to the xAndom cxyatallis4tion o tho gyp~
2. ~he ~oopolymer ~PN i~ no~ des~royed upon . re~alcining o~ the gypsum, and thc ~tructural ao integrity o~ t~e çompos~te a~tor fire expo~ure re~ist~ cxumbling to ~ dsgr~e whlch i~
proportlcnal t~ the amount of geopolyme~ adhe3ivet e~ployedt 3, ~he in~olu~le nature d th~ geopolymer IPN
i~prove~ the performance of ~he composit~ matrix when e~pooed to w~ter, minimlt~ng ~to~taning etCJ
and ~.~bl'd E21Z~ 6 b9 ~3;~ 1`105 NIMa3t~1 gb:i~1 6, ~:ltll`l 11 209~
4. ~h~ ~ddi~i~n of ro~atively inert inorganic additiv~ to t~ ~lurry minl~n~lly ~4f~cts the S qyp~ s cho~n:Lstr~ while providlng ~eed nucleatlon ~ite3 for both gyp811m and geopolymer ~ate~ri~
~x~ple~ o~ ~uch dlspe~oed-pha4e ~nert mal ~:ri~
~re expanded pe~lLte, verm~culat¢~ ~lya3h~
dia~oma~sous earth, etc. ::
A brie~ d~orlption o~ the chemi3t~r o4 g~opoly~r adhe~ives, gyp~ ~lurri~, and mixtu~s thereof ~ill be in~tructiv~. Geopolymer adhe~i.ve~, mix~d to ~ vieoo8ity sulta~l~ fcr worka~ ty in the ~nge o~ 150-200 centipois~, contain abo~t S5% solid~, not ~naludlng the di~p~rsed-phaso additlve (DPA~ matsriAls. ~he3e mlxture~ ~9 alkallne with ~ pR o~ app~ox~nately 11 . 0 11.S, an~ furth~r xoduotion of the pE~ wi hout dllutlon : .
produa~ a wite ~rl~tion of g~lation r~tee. ln additlon, anhydrouEI material whi~h quickly ~sorb~ water wtll al~o produce golation by debyd~tion o~ tl~o geopolyDIer adbes~lve, a~ will the lntrodu~tion of ~olubl~ i c~lciu~ ion~. 81nco the rehydration re~ction of gypsum proceeds in the p~ rAn~e of C-7, modeat quantit~e~ of gyp~ lurry added to the geopolymer adhesi~e will CAU80 rapld ~elation ~nd setting of ~h~ goopoly~ne~.
~hese :ceactlon~ proaeed 50 ~ui~kly that ~dequato ~xin~
~~5T'-1 ~ZTZE~ 6 !9 13~ 1`105 I`lll~lta ~P:90 E6, ~W Tl - 2091~1 - ~2 -lo ~enerally precluded, And attsmpt~ to buffer the pa 0 gypEum to '~he ranga of 11 . a- l l . 5, thereby pr~entlng S gelation by p~ depre~sion, are count~red by th~ presen~0 o~ adequate oalcium ~ttac~ed to the ~ulfate radical .
There~ore, a composite material ~ompri~ing geopcly~n~r ~dhe~lvq w~th minor amount~ of gyp~um a~ an sdditiv~ i~
nat a ~ ble mat~rial for wallboa~d protuction becauso 10 ~rapid ~etti~g o~ tha ~ixture pre61ude~ p~per blendlns and mixing.
The Alternatlve approach, whloh o-ter~om~a~ the a~o~
ideratified di~lcultlo~, is ~o use geopoly~er adhesiveg a~ minor aon~tituent additlves ~o the g~,rp~um slurry.
~h~ tochn~que ha6 b~en ~ound to:
1. sli~inat~ p~ematuro ~etting of th~ gypaum and provide atequata t~e ~or paper wettlng and basrt 2 0 fo~ng;
2. 2~t the ~ddltlon of ~lsporsed-pha~ dditi~
such as flya4h to increa~e the density of the ro~ulting compo~ ion~ to the de ~red level, ther~by pro-r~ding improved bulk material st~ength and ~npro~ed bonding to paper ;~ACing 9heet~t 3 . redu~ th~ 4~nount~ of ralative~ly expen6iYe pO'CA~h ~celerator used in ~:onventional gyp~ ba~
t~E,'91-~ EZ~ZE~ 6 l79 ~3W:1 ~ NOS NI~la3t~a ~P :80 E6, ~IYW 11 2as~
w~llboard slurr~es to decre~e th~ r~sct~on tLme ~or ~tuoco rehy~ratloni 5 4- provide ~de~uate bonding ~ ~tand~rd gyp6Um w~llboard paper faoing ~hcet~ and other ex~erior lamlnat~ng media; eg, polyest~r f&~ric, ~i~re~lAa~
mat~ eto, 5. $mpr~e fire per~or~ance of the re~ulting mat~rial ~y 1ncorporAt,ing tho de~ira~e charact~risticfi of gyp~um, ~hil~ r~duc~ng shrinkAge and warp4ge~
ellm~natin~ crack format~o~ and enhan~ng ~tructur~l lntegrity after recalcinAtion of the ~yp~u~ ~nd 15 6. improve re~lotance to ~o~tenin~ in the pre~nce of wator a~ i9 oh~xacteri~c o~ ordinary gyp8um- ;
ba~d w~llb~ard. . :~
',,' 8avin~ gener~lly de~cri~d the present inYention~ the ~ollow~ng ~peci~ic exa~ are given a~ ~ further illustr~tion th~reof.
A~thouqh exact $ndu~t~iAl formul~tions ~or ~ypsum~ased 2S wallboard mater~al a~ p~opriet~ry~ th~ ~a~or o~mponents ther-of lnclud~ st~roh, pulp paper, lignln, potash, gla4s flbre, stucco, ~a~iv~ gyp~um, wator~ ~oap~ borlc ~~ d EZ~ZE~ 6 ~9 ~3W~ ~ N05 NI~alta ~:80 E~, Ww ~` 2 ~ 9 1 acid, d~xtro~e, and ret~rder ~ n addition to the paper f aclng, trim t~po e~-c . In a laboratory demo~tration o~
the pr~ent invantion, th~ qe~polymar adheaive is form~lA~ed ao a Wet ~lx Additive ~WXA) and ~ Dry Mix Additive (~MA)- Th~ WMA includ~s a su~pe~sion o~ non- :
exp~ndlng alum~nlu~ ~ilicate ol~y or o~her ~ultabl~
cate material, a~ ~ ~hlokenox~ in an ~gueou~
solutl4n of ~n al~ali met~l s~lioate, ~u~fered by A
~ewLa acld 3alt. The DMA lnclud~a finely div~d~d sodium ~illcef~uorlde or zinc oxide an~ cAlciu~ ~etasillcate.
Tho 30dium flu4ros~1icste i5 a ~lowly-dis~olving, p~-lowo~ing and ~u~er~ns chem~cal ~etting agent, the zinc t5 ox~da is also a slowly-dissolving chemioal setting a~ent, and t~e wolla~o~ form o~ o~lci~m mot2silicat~
is added to control shr~nkaga and promote long-term ~trength ~ th~ geopolymer IPN. Fly4~h i~ pre~erable as ~he thlckener matoriAl bec~u~e of it~ low~r cost, but . , kaolinlte, halloy~ite, illite, ~n~ sttApulglte or othar thlcksn6rs Buch a3 wolla~tonlt~ and kaolin may ~e u~ed.
X~olin lnclutes tho hydrou~ alumin~um sllicate clay mlner~l ~roup of ~aterlal~. The ~odium siliaate solution, generally expreosed by the formula Na20-SiO2, 25 and al~o ~nown as water glass (in conoentr~t~d solut~on) ::
or ~odium metaJ~licate, con~i~ts of about 61~ by wei~ht ~f watur, the di~olved ~olld8 lncluding ~lk~li, P~8~ ~ ~Z~ZE~ 6 b9 ~3W~ ~ NOS NIMa3~a 8b:S0 ~6, 2~9~
repreo~ntad by Na20, ~nd Gilio~t~ repr~nted by SiO;~, . .
the sili~ate to ~lkali w~ight ratio rangin~ between 1. 7 5 snd 4.~, with a preferred r~tlo o~ approxlm~tely 3.2.
Solut~on~ o~ ~odium oilica~o uae~ul ir~ the pr ctice o~
~he pre~ent invention inolude be~ween 30 and 40 we~ght p~r~ent of ~olld~ l~pproximately 34 3~ume don~ity), and pr~fera~ly 35-39 wQl~h~ peroent (39 Baun~). Petaa~
10 or lith~u~ ~Llicate Duy b~ sul:st$tut~d ~or the sodlu~n ~iliQate in ~ome ~ltuations. ~ewi~ ~cid m~terials ç~n be MgC12 OJC CaC12~ or a mixture thsreof, in the r~nge ~etween O and 0.4 welqh~ p~rcent; however, N~C
pre~erred . A ounmla~y o~ tho uooful geopolymer adho~e .
1~ oompo~it~ on r~ng~s i~ ~ound in Table I .
~1 Matorial We~aht. ~ (mln1Wei~ht ~ (m~x) Woi la~tonite 5 . 2 2 3 . 6 80tium ~ilicofluorldo 0 . 0 15 . 7 Z~nç oxi~e 1. 3 t . 2 ~_______..________________.._____________________________ Sodiurn oilicate43 . 0 6~ . O
AlkAline earth 2S chlorlde 0.~ 0.4 Water ll.0 16.0 ~aolin 0 . 0 16 . 0 Flya~h 0 . 0 16 . 0 6~ ZIZE~ 6 P9 ~3W~) 'P NOS NI11~1tZ 8P:a6 ~6, WN
-` 2~9~9i ~he ~Lrot two mat~lal~ compr~o the DMA, while the 3econd five c~mpri~e the WMA. ~he zino oxide may b~
used a~ a roplacement ~etting aqent ~or the sodium sili~ofluoride. Finely divided partlola~ o~ zinc o~ide al~o functi~n a~ ~ rQtarder ~n the yyp~u~ wallbo~rd formulatlon~
~ir~t, the al~aline e~rth metal chlo~ide salt is dis~olve~ in water. Alum~nlum aillcate clay ox othsr 3uit~bla sili~ato material i8 mlx~d with 60dLu~ ~illoate ~olution, And after thorough ~l~nding, th~ mot31 chlorLde s~lt ~olutlon is add~d. ~he densl~y o~ the WM~ :
lS i~ typically a~out 1.4 glaa~ ant a~ stated above, ~he ~ :
DM~ i~ typically a dry bl~nd Q~ f~n~ly scr~enod aodlum fluoro~ilicata or zlnc ox~de ~nt ca1cium ~e~a0ilicat~, each o~ wh~ch ar6 relatively in~olublo. ~lya~h, whl~h ~ hi~h ln alumLno-oilicate~, has a large sur~ace area and 6~rve~ a~ ~ nucle~tlon ~it~ and don6ity ~odi~lo~, i~ ..
added to th~ mixture.
~ypi~al ranqes for the ~eopolymier-modlfisd gyp8um wall~oard formulation are s~k ~orth in wct weisht percent in ~blo I~.
6 ~9 ~3~ NoS NI~al~a 8~:80 ~6, .
2Q~
, . ... .
~able ,II :
Com~on~nts W~i~ht S Stuoca 34.5~-54.14 :
Wator 24.43-38.29 Rall mlll a~lex~or 0.09-0.14 St~r~h 0.36~0.56 Pulp paper 0.27-0.43 ~ignin 0.11-0.18 : :
Soap 0.005-0.01 Potash 0.001~0.002 ~las~ ~ib~e 0.11-0.16 _______..__ ________________ ___________________________ WMA 3.70-14.
DMA 1.30-S.20 _____________.. ____________.. _--_----__--------_------------~----------.------ ..
Fly~oh 1.00-20.00 Tho flr~t two aomponente ll~t~d oonstltute the ba~lc gyp~um ~lurry ormulation~ ~r gyp~um w~llboard ~terial, while the next se~n material~ in variou8 co~binat~on~ and with addltlonal ~ ounts of other materlAla ~the ex~t ~ormul~t~n~ quantities and ide~tities b~$ng proprietary with the wall~oard ~nuf~atur~r3) eonstltute le~ than onQ per~ent of the i~itial co~po~ltion. The WMA and DMA e~nstituta th~
r6~lz ~ 6ZIZ6~ 6 ~9 ~3w~ ~ No6 NI~k~ 6P:66 66, ~iw -` 2~9~
geop~olym~3r ~dhe~ive and are added ac~ ording to the t~aA~hings o~ the present lnYention. I!h~ add$tion o~
S ~ly~ ~h to the oompo~sit~on ~s a ~i~perso~d-phase addit~e Ls ~ e~ira~le ~inc~ it 15 quite inexpons~.ve and improva3 the ~uality of the fln~l product. :
~he d~y ingredient~ of ~able II ara ~end~d. These 10 in~r~dients in~lud~ ~'carrh, atuaco, po~ sh, ~ly~8h and on~3-hal~ of ~he gla~ lbre ~ulk. Ona-half o~ the water, the li~nin, and t~he paper pulp, along with th~
remaLnlng one-half of th~ 91~ g~ fi1~ro~ ~re wQll mixsd ~nd dlspers~ad. ~rhe D~ 1~ added to this suspen~ion and 15 the e~ntire 2nixture ~ hl~nded. ~he temper~ture o~ the mlxtur~s 1~ ad~usted to ~bout 100F by the addition ef hot water. Th~ WMA i~ thon ~dded and ~he mixtu~e iB
bl~nd~d. The r~s3ultin~ w~rm, wet mlxt-ure i~ tr~an~ferre~d to another mixing oont~iner whsrs tho ~ ~ixtu~o 19 ao ad~od. ~he semaining water i8 al~o ~dd~d at thi3 ~ime.
All ~ tha ~ompor~ents ~re mlxod for ~ perlod n4t to exceod ~ifteen seconds ~nd tran~ferr~d to p~per-llned f~ning mould~.
25 Refer~n~e will now be made in detail to th~ p~esen~
~r~3~e~re~ embodiDIent~s o~ the ~ nvsnt$on, ~3x~ples of Whi~h are illll0tr~ ted in th~e ac~e~panying dr~ wing~.
t'~ZZ-~ i2~ZI-~ 6 P9 ~J~3~Y0 `8 NOS NIMal~a 6P :~30 0, Wl~
, ` . : , ~ , .. .. . ~ . . . , ~ . -2~91~
~urning ~ow ~o the drawings, Fi~ure 1, ~ur~e 1, illu~trates th6 temperature depandenc~ versu~ time for a typical ~ettin~/cur~ of ~ gyp um w~llboa~d formula~ion. ~;
~he rahyd~tion i4 ~oeentially 40mplete hy a~out 3iX
minute~. ~his is ev~donced by the flattenlng of the temperature profile in that the ~ixture i~ no longer ~anerat~nq additlon~l hea~. At thlo time~ the board ~ 8 ~uf~iciently ~trong to h~ndle 2nd cut.
~gure 1, curva 2 illustrstes a ~imil~r rehydratio~
pr~ ln the la~oratory en~lronment ~or a mixture o~
~ypsum wallboard materials ~nd geopolymer adhe~lve ~ccordlng to the teachings o~ the pre~ent in~ent$4n, exa~pt that th~ ~ly~h, accelerator and retarder hav~
be0n omitted. ~he onset o~ initial setting La ~een to be delAyed about t~n mi~uto~ a~ oppo~ed to that ~f ~igu~e 1, aurv~ l h~r~of, and f ~nal temperatur~ ~chl~ved by the mixtura i~ r~duced, ~a 8 reault o~ the l~rger thermal ~A98 0~ the ~ormulatlon-~igurQ 1~ cuxva 3 shows ~ Yimilar pro~ile to that Lllu~trated in Flgure 1, ¢ur~e 2 herqo~, except that flya5h h~s now been in~luded ln the 0rmulati4n. ~he time ha~ decr~a3ed by ha~. ~he te~peratur~ rl~
~m~llar due to the ~ncrea~ed mass of the adde~ flyaeh~
~~Z'cl E'IZ~ 6 t79 ,Wtl~ ~ N05 NII~laltl~l 6t~ :~3g 6, W~l 11 il ll~R '93 i~l:413 B~LDWIN SON & CI~REY 64 ~1 7321~3 P.~/2 r~
209~
Ao h~s been ~tated hereinabovo t the strength o~ gypsum wallboard compositions i~ directly relatet to the den~ity o~ the fin~l mate~ial. Thl~ den~ity is ln turn ::~
related to the amount o~ water u~ed duri~ th~ mixing ~ :
proces3. Figure 2 show~ the me~sured values of compre~iv~ yield strength ~er~us d0n~ity for ~ v~iety of ~mpleo prepared acaording to tho te~hln~ o~ the prosent inY~ntion with final d~nsitl~s rangi~g from 35 to 46 pcf lepen ~oxe~). Six ætreng~h versu~ de~ity mea~ure~nt~ ~ar typ~aal 0yp8~m ~o~mul~tione a~e plott~d i~ Figure 2 a~ ~ircle~ for compari~on. ~hege are reproduced from CRC Practical and~ook o~ Materlal Scienae, ~able 5.4-11, page 275 th~reof fro~ data o~ : .
Barr~n ~nd Larogue. Mc~t o~ the m~a~urement~ for the aompo~tio~s o~ the pre~ont invention fall i~ the den~ity range between 35 and 58 p~ plotted ~ open 3~uar~ on the ~igure. The three data point~ -~ndiaated by t~iangle3 ha~in~ a~out 41 pa~ density war~ control formulation~ of ~tandart gypswm wallboard mate~ial at 1700 lb~/m~f, whlle the three ~lack square data polnte at a~cut 46 pc~ were vermiculite-doped gypsum/geopolyme~ ~
formulations whare ~lyash wa~ omltted. ~h~s illuRtr~te~ :
that adequate deni~ity can be achieved wlt~ proper selection o~ additiv0s in the formul~tlong of the ~:
pres~nt invention. . ~ ~:
: ' ' ' 2 ~ 9 ~
~-- 2 1 ~
Fi~ure 3 shcws a s:o~pari30n o~ ~he ~3xpo3uxet 0~ a lJ2 ineh gyp~um wallhoaxd ~nd a 1/2 inch wallboard ~abri~t~d acoordi~g to the te~ahing~ of tho pr~ent invontion ha~g id~ntio~l pap~r ~acing ~heet~ to e dir~ct ~lAme. Th~ board matarial ln ea~h c~e wa~
horizontally oriented about 1.5 inc~es a~ovo a proFan~-~i~od Moeker ga6 burner for on~ hour. M~a~lrement thermocouple~ we~e plao~d in ~ontact with the f~ce oxposed to the flame, and on the unexpo~ed facs. ~he ao~ventional ~p6um board Wa6 fully r0caloined, ~ra~ked, warp~d and ~tructurally weakened a~ter the flring period, while the board prepara~ aocording to tho lS toAchin~4 o~ th~ p~sentation lnvontion not only exhibited exoell~nt d~men~ion~l ~t~bllity7 th~t i~, minim~l ahr~nkage, w2rpag~, ~n~ cr~cking, ~ut al~o ~intai~od good ~tru~tural lntegr~ty.
It has therefore ~een fou~d th~t und~r laboratory aondltlon~, addition of S-20g by weight of geopolgmer adhe~lve to conYentional ~ypsum wallboard formul~$ons And the furth~r Qddition of S-lB~ by w~ight of flyash a a DPA i3 ~ucc~ful in pr~duc~ng w~llboard having desired oharact~rigtic~. In the aonc~ntration~ ::
;nve~tigated, the geopolymer act~ as ~ dilu'c~ i~purity and do~s not up~t the c~ystal growth o~ the gypsUTQ and !
t~~7Z'd ZIZE~! 6 ~9 ,~3W~ ~ NOS NIllalt:a 05:20 6, ;~lt~l^l 1~ !
2091~1 at~endan~ Attach~Qnt o~ the aore ~atexie~l to ~ing ~heet material S
~he ~ollowing ~axamplea illustrate the application o~ the t~aching~ cf the prssent in~ventiorl in ~ cen~entional qypsum wall~o~r~ pl~nt. ~h~ ~r~n~2y gypau~n 31ur~y rlow r~te in the plAr~t e~ ployed wa~ 212~ /~n. ~tes 10 reduoihg tha ~yp~u~n flow ~ata, the geepolytller 2dhe~ive wa~ ~dded AO hr~e separat~ aompoQen~: sodiu~ ~Lliaata solut~on~ watar and DMBI.~ A blend c DMA and the wlid aompor~ents o~ WMA, in amount~ lluch th~t the flnAl flow rat~ wa~ ag~in 2124 lbG/min. 1~ torial~ w~r~ ~dd~d 1$ to the gyp8Um 31urry throllgh a hlgh-~hea~ pin mlx~r which achieved uniform ~ix~ng within ~ s~cond6. The re3ultlng seopolym~r-modi~d gyp911m wallboard m~terl~l w9~ prooe~sed accordin~ to osdinary plant proced~re~.
In aome experiments, addlt~onal flyash ~8 added to 20 lmprove the re~ulting wallboA~d product and reduc~
over~l 1 m~t~rial~ costa .
'': ' ~ea~ ,~ ",, 25 !I!he ~ um flow rate w~ reduced to 2Q17.a lb~/min in ordor to add 106.2 lb8/~ of geopolymer ~dhe~ve as S7.û lb~/~in of sodium 6il~cate solution, 10,.4 }b~/min of ~Xt~a wator, ~nd 34.8 1~3/ntin o~ DM~
~E.'SZ-d E21ZE~! 6 b9 ,W1~0 ~ NOS NIllal~EI 05 :80 E6, Wl^l 1 20~91 :
fl~rash:
S Alons~ with ~he ~dtation o~ the mat~rl~ g de~crib~d ln A.l 5% of flya3h w~ added a~ f~llow~:
Th~ gypoum ~low rate w~s radu~ed to 1960.9 l~o~in~ and Bq.1 lbstmln of ~odlum sllicate 301u~io~, ~3.7 l~tmln of extra wator, 33.1 l~s~man of D~B~ ~nd 106.2 lbx/~in o~ ~ly~h w~r~ added.
~l~ash:
Along wlth the ~ttition of ~-h~ mat~rial8 a8 de~ribed in A.l, 10% o~ a~h ~8 add~d ~ff ~ollowo~
The gypsum flow rate w~ roduaed to 1~16.0 lb~min, ~nd ;~
51.3 lbs/mln of ~odlum ~ilicate colut~on, 1~.0 l~min of extra wat~r, 31.3 l~s/min of D~B~ and 212.4 lb~min o~ h wexe ad~ed.
~.1 90~ oY~pm lurrv and 10%_~eoDOlYmer adho~lve~ :
Th~ gyp~um ~low rat~ wa~ red~ood to 1911.6 lb~/min ln ; .
2i ordqr to add 114.0 lb~Jmin of ~odium siliaate ~olut~on, 28~8 lb~/min ~ extra watsr and 69.7 lb~/mln ~M~L.
~E~9Z-d EZ~ZE~ 6 b9 ~3W~ ~ NOS NIMa3~ S :813 E6, W~
~ 2~9~
~ , ` . .
Along with the ad~ltion of the materials ae described in B.1~ 5~ 0~ A9h was added as follow~
The S~pDUm flow rate was reduced to 181C.0 lb~/min, and 108.3 lbs~mln o~ sodiu~n 6ilicata ~olut~on, 27.4 l~s/min o~ oxtra wa~or~ 66.2 l~Jm~n o~ DMB~ and 106.2 l~s/min o~ ~lya~h w~r~ adtod.
~ ~ , 0~ ~1YB~h:
lS A~ong with the ~dd~tion of the materi~ls a~ described in ~.1, 10~ cf flya~h was added ~9 follows~
The ~yp~ low rate w~ r~duced to 1720.4 lb~/~in, and ;~, 102.6 lb~/~in o~ sodiu~ s~licate ~olution, 2s.s lbo/min of extra wa'car, 62.7 lbs/~ln o~ and 212.4 l~
of ~ly~h ~re added.
'rO~t4 on the resultlng wallko~rd de~on~tr~ted that th~ ~:
atdltlon o~ geopolym~r adh~ive and ~lya~h to ~tandard 25 gypeum olurr~ ln a wallboard plant environment produc~d ~u~erior quallty wall~oard mate~l~13 hav1ng ~imilar ch~racterl~ti~s to ~hat produced in the laboratory d~non~tr~t~on of ~xampl~ 1.
i :
t~~Z-d E'~ZE~ 6 t79 ~3~ NOS NIP1a~ 5 :80 ~6, ;Y;~
2~g~
:
~he foregolng d2scription o~ ~everal pre~erred e~badiments o~ the invent1OIl ha~ been pr~ent~d ~or S purposes o ill~tratlon and description. It 1~ not intended to be exhau~tl~e ox to llmit the invention to the preaise fcr~ d1s~les~d ~nd o~viou61y many modi~icAt~on~ ~nd varLAtion~ are pos~ible in light o1' the ~ov~ teachlng. The em~odi~onts were ~hosen ~nd de~ar~bed in order to b~t expla~ the p~nciples o~ the invontio~ and it~ praotical ~pplic~ion to thareby onable oth~r~ ~killed in the art to be~t utllL~e tha invent~on in various embodlment~ and with ~riou~
~odi~i~ation~ ~B 4re ~uited to the par~icular uso oontemplated~
~here in the foregoing deacrlption referenoe h~s ~een made to ~peoiflc oomponent~ or intoge~ of the lnvention h~vi~g known oqu~v~lent~ ~hen suoh ~uival~nt3 ~re 20 h~rein in~orpor~tad a~ ~ individuAlly ~et ~orth. .
Althcu~h this in~ention has bee~ d2scri~ed by ~y exhmpl~ and with r~fer~nae to po~iblo embodiment~
thereof it i~ to ~e under~tood that modific~tions or 2S improvem~ntu mQy be m~de ther~to withou.t depar~ing ~ro~
the s¢ope o~ the 1nvantien a~ deflned ~n the appended claim~.
~~82 'c~ 8212~ 6 b9 ,~3W~ ~ NOS NIM~:13~E[ IS :80 6, 2~W 1
~x~ple~ o~ ~uch dlspe~oed-pha4e ~nert mal ~:ri~
~re expanded pe~lLte, verm~culat¢~ ~lya3h~
dia~oma~sous earth, etc. ::
A brie~ d~orlption o~ the chemi3t~r o4 g~opoly~r adhe~ives, gyp~ ~lurri~, and mixtu~s thereof ~ill be in~tructiv~. Geopolymer adhe~i.ve~, mix~d to ~ vieoo8ity sulta~l~ fcr worka~ ty in the ~nge o~ 150-200 centipois~, contain abo~t S5% solid~, not ~naludlng the di~p~rsed-phaso additlve (DPA~ matsriAls. ~he3e mlxture~ ~9 alkallne with ~ pR o~ app~ox~nately 11 . 0 11.S, an~ furth~r xoduotion of the pE~ wi hout dllutlon : .
produa~ a wite ~rl~tion of g~lation r~tee. ln additlon, anhydrouEI material whi~h quickly ~sorb~ water wtll al~o produce golation by debyd~tion o~ tl~o geopolyDIer adbes~lve, a~ will the lntrodu~tion of ~olubl~ i c~lciu~ ion~. 81nco the rehydration re~ction of gypsum proceeds in the p~ rAn~e of C-7, modeat quantit~e~ of gyp~ lurry added to the geopolymer adhesi~e will CAU80 rapld ~elation ~nd setting of ~h~ goopoly~ne~.
~hese :ceactlon~ proaeed 50 ~ui~kly that ~dequato ~xin~
~~5T'-1 ~ZTZE~ 6 !9 13~ 1`105 I`lll~lta ~P:90 E6, ~W Tl - 2091~1 - ~2 -lo ~enerally precluded, And attsmpt~ to buffer the pa 0 gypEum to '~he ranga of 11 . a- l l . 5, thereby pr~entlng S gelation by p~ depre~sion, are count~red by th~ presen~0 o~ adequate oalcium ~ttac~ed to the ~ulfate radical .
There~ore, a composite material ~ompri~ing geopcly~n~r ~dhe~lvq w~th minor amount~ of gyp~um a~ an sdditiv~ i~
nat a ~ ble mat~rial for wallboa~d protuction becauso 10 ~rapid ~etti~g o~ tha ~ixture pre61ude~ p~per blendlns and mixing.
The Alternatlve approach, whloh o-ter~om~a~ the a~o~
ideratified di~lcultlo~, is ~o use geopoly~er adhesiveg a~ minor aon~tituent additlves ~o the g~,rp~um slurry.
~h~ tochn~que ha6 b~en ~ound to:
1. sli~inat~ p~ematuro ~etting of th~ gypaum and provide atequata t~e ~or paper wettlng and basrt 2 0 fo~ng;
2. 2~t the ~ddltlon of ~lsporsed-pha~ dditi~
such as flya4h to increa~e the density of the ro~ulting compo~ ion~ to the de ~red level, ther~by pro-r~ding improved bulk material st~ength and ~npro~ed bonding to paper ;~ACing 9heet~t 3 . redu~ th~ 4~nount~ of ralative~ly expen6iYe pO'CA~h ~celerator used in ~:onventional gyp~ ba~
t~E,'91-~ EZ~ZE~ 6 l79 ~3W:1 ~ NOS NI~la3t~a ~P :80 E6, ~IYW 11 2as~
w~llboard slurr~es to decre~e th~ r~sct~on tLme ~or ~tuoco rehy~ratloni 5 4- provide ~de~uate bonding ~ ~tand~rd gyp6Um w~llboard paper faoing ~hcet~ and other ex~erior lamlnat~ng media; eg, polyest~r f&~ric, ~i~re~lAa~
mat~ eto, 5. $mpr~e fire per~or~ance of the re~ulting mat~rial ~y 1ncorporAt,ing tho de~ira~e charact~risticfi of gyp~um, ~hil~ r~duc~ng shrinkAge and warp4ge~
ellm~natin~ crack format~o~ and enhan~ng ~tructur~l lntegrity after recalcinAtion of the ~yp~u~ ~nd 15 6. improve re~lotance to ~o~tenin~ in the pre~nce of wator a~ i9 oh~xacteri~c o~ ordinary gyp8um- ;
ba~d w~llb~ard. . :~
',,' 8avin~ gener~lly de~cri~d the present inYention~ the ~ollow~ng ~peci~ic exa~ are given a~ ~ further illustr~tion th~reof.
A~thouqh exact $ndu~t~iAl formul~tions ~or ~ypsum~ased 2S wallboard mater~al a~ p~opriet~ry~ th~ ~a~or o~mponents ther-of lnclud~ st~roh, pulp paper, lignln, potash, gla4s flbre, stucco, ~a~iv~ gyp~um, wator~ ~oap~ borlc ~~ d EZ~ZE~ 6 ~9 ~3W~ ~ N05 NI~alta ~:80 E~, Ww ~` 2 ~ 9 1 acid, d~xtro~e, and ret~rder ~ n addition to the paper f aclng, trim t~po e~-c . In a laboratory demo~tration o~
the pr~ent invantion, th~ qe~polymar adheaive is form~lA~ed ao a Wet ~lx Additive ~WXA) and ~ Dry Mix Additive (~MA)- Th~ WMA includ~s a su~pe~sion o~ non- :
exp~ndlng alum~nlu~ ~ilicate ol~y or o~her ~ultabl~
cate material, a~ ~ ~hlokenox~ in an ~gueou~
solutl4n of ~n al~ali met~l s~lioate, ~u~fered by A
~ewLa acld 3alt. The DMA lnclud~a finely div~d~d sodium ~illcef~uorlde or zinc oxide an~ cAlciu~ ~etasillcate.
Tho 30dium flu4ros~1icste i5 a ~lowly-dis~olving, p~-lowo~ing and ~u~er~ns chem~cal ~etting agent, the zinc t5 ox~da is also a slowly-dissolving chemioal setting a~ent, and t~e wolla~o~ form o~ o~lci~m mot2silicat~
is added to control shr~nkaga and promote long-term ~trength ~ th~ geopolymer IPN. Fly4~h i~ pre~erable as ~he thlckener matoriAl bec~u~e of it~ low~r cost, but . , kaolinlte, halloy~ite, illite, ~n~ sttApulglte or othar thlcksn6rs Buch a3 wolla~tonlt~ and kaolin may ~e u~ed.
X~olin lnclutes tho hydrou~ alumin~um sllicate clay mlner~l ~roup of ~aterlal~. The ~odium siliaate solution, generally expreosed by the formula Na20-SiO2, 25 and al~o ~nown as water glass (in conoentr~t~d solut~on) ::
or ~odium metaJ~licate, con~i~ts of about 61~ by wei~ht ~f watur, the di~olved ~olld8 lncluding ~lk~li, P~8~ ~ ~Z~ZE~ 6 b9 ~3W~ ~ NOS NIMa3~a 8b:S0 ~6, 2~9~
repreo~ntad by Na20, ~nd Gilio~t~ repr~nted by SiO;~, . .
the sili~ate to ~lkali w~ight ratio rangin~ between 1. 7 5 snd 4.~, with a preferred r~tlo o~ approxlm~tely 3.2.
Solut~on~ o~ ~odium oilica~o uae~ul ir~ the pr ctice o~
~he pre~ent invention inolude be~ween 30 and 40 we~ght p~r~ent of ~olld~ l~pproximately 34 3~ume don~ity), and pr~fera~ly 35-39 wQl~h~ peroent (39 Baun~). Petaa~
10 or lith~u~ ~Llicate Duy b~ sul:st$tut~d ~or the sodlu~n ~iliQate in ~ome ~ltuations. ~ewi~ ~cid m~terials ç~n be MgC12 OJC CaC12~ or a mixture thsreof, in the r~nge ~etween O and 0.4 welqh~ p~rcent; however, N~C
pre~erred . A ounmla~y o~ tho uooful geopolymer adho~e .
1~ oompo~it~ on r~ng~s i~ ~ound in Table I .
~1 Matorial We~aht. ~ (mln1Wei~ht ~ (m~x) Woi la~tonite 5 . 2 2 3 . 6 80tium ~ilicofluorldo 0 . 0 15 . 7 Z~nç oxi~e 1. 3 t . 2 ~_______..________________.._____________________________ Sodiurn oilicate43 . 0 6~ . O
AlkAline earth 2S chlorlde 0.~ 0.4 Water ll.0 16.0 ~aolin 0 . 0 16 . 0 Flya~h 0 . 0 16 . 0 6~ ZIZE~ 6 P9 ~3W~) 'P NOS NI11~1tZ 8P:a6 ~6, WN
-` 2~9~9i ~he ~Lrot two mat~lal~ compr~o the DMA, while the 3econd five c~mpri~e the WMA. ~he zino oxide may b~
used a~ a roplacement ~etting aqent ~or the sodium sili~ofluoride. Finely divided partlola~ o~ zinc o~ide al~o functi~n a~ ~ rQtarder ~n the yyp~u~ wallbo~rd formulatlon~
~ir~t, the al~aline e~rth metal chlo~ide salt is dis~olve~ in water. Alum~nlum aillcate clay ox othsr 3uit~bla sili~ato material i8 mlx~d with 60dLu~ ~illoate ~olution, And after thorough ~l~nding, th~ mot31 chlorLde s~lt ~olutlon is add~d. ~he densl~y o~ the WM~ :
lS i~ typically a~out 1.4 glaa~ ant a~ stated above, ~he ~ :
DM~ i~ typically a dry bl~nd Q~ f~n~ly scr~enod aodlum fluoro~ilicata or zlnc ox~de ~nt ca1cium ~e~a0ilicat~, each o~ wh~ch ar6 relatively in~olublo. ~lya~h, whl~h ~ hi~h ln alumLno-oilicate~, has a large sur~ace area and 6~rve~ a~ ~ nucle~tlon ~it~ and don6ity ~odi~lo~, i~ ..
added to th~ mixture.
~ypi~al ranqes for the ~eopolymier-modlfisd gyp8um wall~oard formulation are s~k ~orth in wct weisht percent in ~blo I~.
6 ~9 ~3~ NoS NI~al~a 8~:80 ~6, .
2Q~
, . ... .
~able ,II :
Com~on~nts W~i~ht S Stuoca 34.5~-54.14 :
Wator 24.43-38.29 Rall mlll a~lex~or 0.09-0.14 St~r~h 0.36~0.56 Pulp paper 0.27-0.43 ~ignin 0.11-0.18 : :
Soap 0.005-0.01 Potash 0.001~0.002 ~las~ ~ib~e 0.11-0.16 _______..__ ________________ ___________________________ WMA 3.70-14.
DMA 1.30-S.20 _____________.. ____________.. _--_----__--------_------------~----------.------ ..
Fly~oh 1.00-20.00 Tho flr~t two aomponente ll~t~d oonstltute the ba~lc gyp~um ~lurry ormulation~ ~r gyp~um w~llboard ~terial, while the next se~n material~ in variou8 co~binat~on~ and with addltlonal ~ ounts of other materlAla ~the ex~t ~ormul~t~n~ quantities and ide~tities b~$ng proprietary with the wall~oard ~nuf~atur~r3) eonstltute le~ than onQ per~ent of the i~itial co~po~ltion. The WMA and DMA e~nstituta th~
r6~lz ~ 6ZIZ6~ 6 ~9 ~3w~ ~ No6 NI~k~ 6P:66 66, ~iw -` 2~9~
geop~olym~3r ~dhe~ive and are added ac~ ording to the t~aA~hings o~ the present lnYention. I!h~ add$tion o~
S ~ly~ ~h to the oompo~sit~on ~s a ~i~perso~d-phase addit~e Ls ~ e~ira~le ~inc~ it 15 quite inexpons~.ve and improva3 the ~uality of the fln~l product. :
~he d~y ingredient~ of ~able II ara ~end~d. These 10 in~r~dients in~lud~ ~'carrh, atuaco, po~ sh, ~ly~8h and on~3-hal~ of ~he gla~ lbre ~ulk. Ona-half o~ the water, the li~nin, and t~he paper pulp, along with th~
remaLnlng one-half of th~ 91~ g~ fi1~ro~ ~re wQll mixsd ~nd dlspers~ad. ~rhe D~ 1~ added to this suspen~ion and 15 the e~ntire 2nixture ~ hl~nded. ~he temper~ture o~ the mlxtur~s 1~ ad~usted to ~bout 100F by the addition ef hot water. Th~ WMA i~ thon ~dded and ~he mixtu~e iB
bl~nd~d. The r~s3ultin~ w~rm, wet mlxt-ure i~ tr~an~ferre~d to another mixing oont~iner whsrs tho ~ ~ixtu~o 19 ao ad~od. ~he semaining water i8 al~o ~dd~d at thi3 ~ime.
All ~ tha ~ompor~ents ~re mlxod for ~ perlod n4t to exceod ~ifteen seconds ~nd tran~ferr~d to p~per-llned f~ning mould~.
25 Refer~n~e will now be made in detail to th~ p~esen~
~r~3~e~re~ embodiDIent~s o~ the ~ nvsnt$on, ~3x~ples of Whi~h are illll0tr~ ted in th~e ac~e~panying dr~ wing~.
t'~ZZ-~ i2~ZI-~ 6 P9 ~J~3~Y0 `8 NOS NIMal~a 6P :~30 0, Wl~
, ` . : , ~ , .. .. . ~ . . . , ~ . -2~91~
~urning ~ow ~o the drawings, Fi~ure 1, ~ur~e 1, illu~trates th6 temperature depandenc~ versu~ time for a typical ~ettin~/cur~ of ~ gyp um w~llboa~d formula~ion. ~;
~he rahyd~tion i4 ~oeentially 40mplete hy a~out 3iX
minute~. ~his is ev~donced by the flattenlng of the temperature profile in that the ~ixture i~ no longer ~anerat~nq additlon~l hea~. At thlo time~ the board ~ 8 ~uf~iciently ~trong to h~ndle 2nd cut.
~gure 1, curva 2 illustrstes a ~imil~r rehydratio~
pr~ ln the la~oratory en~lronment ~or a mixture o~
~ypsum wallboard materials ~nd geopolymer adhe~lve ~ccordlng to the teachings o~ the pre~ent in~ent$4n, exa~pt that th~ ~ly~h, accelerator and retarder hav~
be0n omitted. ~he onset o~ initial setting La ~een to be delAyed about t~n mi~uto~ a~ oppo~ed to that ~f ~igu~e 1, aurv~ l h~r~of, and f ~nal temperatur~ ~chl~ved by the mixtura i~ r~duced, ~a 8 reault o~ the l~rger thermal ~A98 0~ the ~ormulatlon-~igurQ 1~ cuxva 3 shows ~ Yimilar pro~ile to that Lllu~trated in Flgure 1, ¢ur~e 2 herqo~, except that flya5h h~s now been in~luded ln the 0rmulati4n. ~he time ha~ decr~a3ed by ha~. ~he te~peratur~ rl~
~m~llar due to the ~ncrea~ed mass of the adde~ flyaeh~
~~Z'cl E'IZ~ 6 t79 ,Wtl~ ~ N05 NII~laltl~l 6t~ :~3g 6, W~l 11 il ll~R '93 i~l:413 B~LDWIN SON & CI~REY 64 ~1 7321~3 P.~/2 r~
209~
Ao h~s been ~tated hereinabovo t the strength o~ gypsum wallboard compositions i~ directly relatet to the den~ity o~ the fin~l mate~ial. Thl~ den~ity is ln turn ::~
related to the amount o~ water u~ed duri~ th~ mixing ~ :
proces3. Figure 2 show~ the me~sured values of compre~iv~ yield strength ~er~us d0n~ity for ~ v~iety of ~mpleo prepared acaording to tho te~hln~ o~ the prosent inY~ntion with final d~nsitl~s rangi~g from 35 to 46 pcf lepen ~oxe~). Six ætreng~h versu~ de~ity mea~ure~nt~ ~ar typ~aal 0yp8~m ~o~mul~tione a~e plott~d i~ Figure 2 a~ ~ircle~ for compari~on. ~hege are reproduced from CRC Practical and~ook o~ Materlal Scienae, ~able 5.4-11, page 275 th~reof fro~ data o~ : .
Barr~n ~nd Larogue. Mc~t o~ the m~a~urement~ for the aompo~tio~s o~ the pre~ont invention fall i~ the den~ity range between 35 and 58 p~ plotted ~ open 3~uar~ on the ~igure. The three data point~ -~ndiaated by t~iangle3 ha~in~ a~out 41 pa~ density war~ control formulation~ of ~tandart gypswm wallboard mate~ial at 1700 lb~/m~f, whlle the three ~lack square data polnte at a~cut 46 pc~ were vermiculite-doped gypsum/geopolyme~ ~
formulations whare ~lyash wa~ omltted. ~h~s illuRtr~te~ :
that adequate deni~ity can be achieved wlt~ proper selection o~ additiv0s in the formul~tlong of the ~:
pres~nt invention. . ~ ~:
: ' ' ' 2 ~ 9 ~
~-- 2 1 ~
Fi~ure 3 shcws a s:o~pari30n o~ ~he ~3xpo3uxet 0~ a lJ2 ineh gyp~um wallhoaxd ~nd a 1/2 inch wallboard ~abri~t~d acoordi~g to the te~ahing~ of tho pr~ent invontion ha~g id~ntio~l pap~r ~acing ~heet~ to e dir~ct ~lAme. Th~ board matarial ln ea~h c~e wa~
horizontally oriented about 1.5 inc~es a~ovo a proFan~-~i~od Moeker ga6 burner for on~ hour. M~a~lrement thermocouple~ we~e plao~d in ~ontact with the f~ce oxposed to the flame, and on the unexpo~ed facs. ~he ao~ventional ~p6um board Wa6 fully r0caloined, ~ra~ked, warp~d and ~tructurally weakened a~ter the flring period, while the board prepara~ aocording to tho lS toAchin~4 o~ th~ p~sentation lnvontion not only exhibited exoell~nt d~men~ion~l ~t~bllity7 th~t i~, minim~l ahr~nkage, w2rpag~, ~n~ cr~cking, ~ut al~o ~intai~od good ~tru~tural lntegr~ty.
It has therefore ~een fou~d th~t und~r laboratory aondltlon~, addition of S-20g by weight of geopolgmer adhe~lve to conYentional ~ypsum wallboard formul~$ons And the furth~r Qddition of S-lB~ by w~ight of flyash a a DPA i3 ~ucc~ful in pr~duc~ng w~llboard having desired oharact~rigtic~. In the aonc~ntration~ ::
;nve~tigated, the geopolymer act~ as ~ dilu'c~ i~purity and do~s not up~t the c~ystal growth o~ the gypsUTQ and !
t~~7Z'd ZIZE~! 6 ~9 ,~3W~ ~ NOS NIllalt:a 05:20 6, ;~lt~l^l 1~ !
2091~1 at~endan~ Attach~Qnt o~ the aore ~atexie~l to ~ing ~heet material S
~he ~ollowing ~axamplea illustrate the application o~ the t~aching~ cf the prssent in~ventiorl in ~ cen~entional qypsum wall~o~r~ pl~nt. ~h~ ~r~n~2y gypau~n 31ur~y rlow r~te in the plAr~t e~ ployed wa~ 212~ /~n. ~tes 10 reduoihg tha ~yp~u~n flow ~ata, the geepolytller 2dhe~ive wa~ ~dded AO hr~e separat~ aompoQen~: sodiu~ ~Lliaata solut~on~ watar and DMBI.~ A blend c DMA and the wlid aompor~ents o~ WMA, in amount~ lluch th~t the flnAl flow rat~ wa~ ag~in 2124 lbG/min. 1~ torial~ w~r~ ~dd~d 1$ to the gyp8Um 31urry throllgh a hlgh-~hea~ pin mlx~r which achieved uniform ~ix~ng within ~ s~cond6. The re3ultlng seopolym~r-modi~d gyp911m wallboard m~terl~l w9~ prooe~sed accordin~ to osdinary plant proced~re~.
In aome experiments, addlt~onal flyash ~8 added to 20 lmprove the re~ulting wallboA~d product and reduc~
over~l 1 m~t~rial~ costa .
'': ' ~ea~ ,~ ",, 25 !I!he ~ um flow rate w~ reduced to 2Q17.a lb~/min in ordor to add 106.2 lb8/~ of geopolymer ~dhe~ve as S7.û lb~/~in of sodium 6il~cate solution, 10,.4 }b~/min of ~Xt~a wator, ~nd 34.8 1~3/ntin o~ DM~
~E.'SZ-d E21ZE~! 6 b9 ,W1~0 ~ NOS NIllal~EI 05 :80 E6, Wl^l 1 20~91 :
fl~rash:
S Alons~ with ~he ~dtation o~ the mat~rl~ g de~crib~d ln A.l 5% of flya3h w~ added a~ f~llow~:
Th~ gypoum ~low rate w~s radu~ed to 1960.9 l~o~in~ and Bq.1 lbstmln of ~odlum sllicate 301u~io~, ~3.7 l~tmln of extra wator, 33.1 l~s~man of D~B~ ~nd 106.2 lbx/~in o~ ~ly~h w~r~ added.
~l~ash:
Along wlth the ~ttition of ~-h~ mat~rial8 a8 de~ribed in A.l, 10% o~ a~h ~8 add~d ~ff ~ollowo~
The gypsum flow rate w~ roduaed to 1~16.0 lb~min, ~nd ;~
51.3 lbs/mln of ~odlum ~ilicate colut~on, 1~.0 l~min of extra wat~r, 31.3 l~s/min of D~B~ and 212.4 lb~min o~ h wexe ad~ed.
~.1 90~ oY~pm lurrv and 10%_~eoDOlYmer adho~lve~ :
Th~ gyp~um ~low rat~ wa~ red~ood to 1911.6 lb~/min ln ; .
2i ordqr to add 114.0 lb~Jmin of ~odium siliaate ~olut~on, 28~8 lb~/min ~ extra watsr and 69.7 lb~/mln ~M~L.
~E~9Z-d EZ~ZE~ 6 b9 ~3W~ ~ NOS NIMa3~ S :813 E6, W~
~ 2~9~
~ , ` . .
Along with the ad~ltion of the materials ae described in B.1~ 5~ 0~ A9h was added as follow~
The S~pDUm flow rate was reduced to 181C.0 lb~/min, and 108.3 lbs~mln o~ sodiu~n 6ilicata ~olut~on, 27.4 l~s/min o~ oxtra wa~or~ 66.2 l~Jm~n o~ DMB~ and 106.2 l~s/min o~ ~lya~h w~r~ adtod.
~ ~ , 0~ ~1YB~h:
lS A~ong with the ~dd~tion of the materi~ls a~ described in ~.1, 10~ cf flya~h was added ~9 follows~
The ~yp~ low rate w~ r~duced to 1720.4 lb~/~in, and ;~, 102.6 lb~/~in o~ sodiu~ s~licate ~olution, 2s.s lbo/min of extra wa'car, 62.7 lbs/~ln o~ and 212.4 l~
of ~ly~h ~re added.
'rO~t4 on the resultlng wallko~rd de~on~tr~ted that th~ ~:
atdltlon o~ geopolym~r adh~ive and ~lya~h to ~tandard 25 gypeum olurr~ ln a wallboard plant environment produc~d ~u~erior quallty wall~oard mate~l~13 hav1ng ~imilar ch~racterl~ti~s to ~hat produced in the laboratory d~non~tr~t~on of ~xampl~ 1.
i :
t~~Z-d E'~ZE~ 6 t79 ~3~ NOS NIP1a~ 5 :80 ~6, ;Y;~
2~g~
:
~he foregolng d2scription o~ ~everal pre~erred e~badiments o~ the invent1OIl ha~ been pr~ent~d ~or S purposes o ill~tratlon and description. It 1~ not intended to be exhau~tl~e ox to llmit the invention to the preaise fcr~ d1s~les~d ~nd o~viou61y many modi~icAt~on~ ~nd varLAtion~ are pos~ible in light o1' the ~ov~ teachlng. The em~odi~onts were ~hosen ~nd de~ar~bed in order to b~t expla~ the p~nciples o~ the invontio~ and it~ praotical ~pplic~ion to thareby onable oth~r~ ~killed in the art to be~t utllL~e tha invent~on in various embodlment~ and with ~riou~
~odi~i~ation~ ~B 4re ~uited to the par~icular uso oontemplated~
~here in the foregoing deacrlption referenoe h~s ~een made to ~peoiflc oomponent~ or intoge~ of the lnvention h~vi~g known oqu~v~lent~ ~hen suoh ~uival~nt3 ~re 20 h~rein in~orpor~tad a~ ~ individuAlly ~et ~orth. .
Althcu~h this in~ention has bee~ d2scri~ed by ~y exhmpl~ and with r~fer~nae to po~iblo embodiment~
thereof it i~ to ~e under~tood that modific~tions or 2S improvem~ntu mQy be m~de ther~to withou.t depar~ing ~ro~
the s¢ope o~ the 1nvantien a~ deflned ~n the appended claim~.
~~82 'c~ 8212~ 6 b9 ,~3W~ ~ NOS NIM~:13~E[ IS :80 6, 2~W 1
Claims (10)
1. A gypsum wallboard material having improved fire and water resistance produced from combining a self-hardening mixture comprising a geopolymer adhesive with a gypsum wallboard slurry, characterised in that said geopolymer adhesive comprises a soluble alkali metal silicate solution, a chemical setting agent and a thickening agent.
2. A gypsum wallboard material as claimed in Claim 1, characterised in that said geopolymer adhesive further comprises a strengthening agent.
3. A gypsum wallboard material as claimed in Claim 2, characterised in that said strengthening agent includes calcium metasilicate.
4. A gypsum wallboard material as claimed in Claim 1, characterised in that said soluble alkali metal silicate is selected from the group consisting of sodium silicate, potassium silicate and lithium silicate.
5. A gypsum wallboard material as claimed in Claim 1, characterised in that said thickening agent includes hydrous aluminium silicate clay.
6. A gypsum wallboard material as claimed in Claim 1, characterised in that said chemical setting agent includes sodium fluorosilicate.
7. A gypsum wallboard material as claimed in Claim 1, characterised in that said chemical setting agent includes zinc oxide.
8. A gypsum wallboard material as claimed in Claim 1, characterised in that a sufficient amount of said geopolymer adhesive is present to form an interpenetrating network which bonds, supports and provides improved fire and water resistance to said gypsum board formulation.
9. A gypsum board material as claimed in Claim 1, characterised in that said geopolymer adhesive further includes a pH-lowering and buffering agent.
10. A method for producing a gypsum wallboard material having improved fire and water resistance, said method characterised in the steps of:
a) combining a self-hardening mixture comprising gypsum wallboard slurry with a geopolymer adhesive, said geopolymer adhesive comprising a soluble alkali metal silicate solution, a thickening agent, and a chemical setting agent; and b) permitting the mixture resulting therefrom to harden.
a) combining a self-hardening mixture comprising gypsum wallboard slurry with a geopolymer adhesive, said geopolymer adhesive comprising a soluble alkali metal silicate solution, a thickening agent, and a chemical setting agent; and b) permitting the mixture resulting therefrom to harden.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/635,735 US5194091A (en) | 1990-12-26 | 1990-12-26 | Geopolymer-modified, gypsum-based construction materials |
CA 2091491 CA2091491A1 (en) | 1990-12-26 | 1993-03-11 | Geopolymer-modified, gypsum-based construction material |
EP19930301837 EP0614858A1 (en) | 1990-12-26 | 1993-03-11 | Geopolymer-modified, gypsum-based construction material |
CN93109898A CN1097198A (en) | 1990-12-26 | 1993-07-05 | Advanced geopolymer composites |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/635,735 US5194091A (en) | 1990-12-26 | 1990-12-26 | Geopolymer-modified, gypsum-based construction materials |
CA 2091491 CA2091491A1 (en) | 1990-12-26 | 1993-03-11 | Geopolymer-modified, gypsum-based construction material |
EP19930301837 EP0614858A1 (en) | 1990-12-26 | 1993-03-11 | Geopolymer-modified, gypsum-based construction material |
CN93109898A CN1097198A (en) | 1990-12-26 | 1993-07-05 | Advanced geopolymer composites |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2091491A1 true CA2091491A1 (en) | 1994-09-12 |
Family
ID=36829840
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2091491 Abandoned CA2091491A1 (en) | 1990-12-26 | 1993-03-11 | Geopolymer-modified, gypsum-based construction material |
Country Status (4)
Country | Link |
---|---|
US (1) | US5194091A (en) |
EP (1) | EP0614858A1 (en) |
CN (1) | CN1097198A (en) |
CA (1) | CA2091491A1 (en) |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2659320B1 (en) * | 1990-03-07 | 1992-07-03 | Davidovics Michel | FLUORO-ALUMINO-SILICATE GEOPOLYMERIC BINDER AND PROCESS FOR OBTAINING SAME. |
DE69105958T2 (en) * | 1990-03-07 | 1995-08-10 | Nicolas Davidovits | METHOD FOR PRODUCING AN ALUMINUM SILICATE GEOPOLYMER AND PRODUCTS PRODUCED THEREOF. |
US5194091A (en) * | 1990-12-26 | 1993-03-16 | The Hera Corporation | Geopolymer-modified, gypsum-based construction materials |
FR2730227B1 (en) * | 1995-02-03 | 1997-03-14 | Pechiney Recherche | COMPOSITION FOR COATING CARBON PRODUCTS AND COATING |
US5492562A (en) * | 1995-02-07 | 1996-02-20 | Pettinato; Dana M. | Low freezing point roofing shingle containing a chloride salt |
AU748813B2 (en) * | 1997-05-05 | 2002-06-13 | Corn Products International, Inc. | Adhesive compositions for corrugated boxes |
US6471767B1 (en) | 1999-10-15 | 2002-10-29 | American International Materials, Ltd. | Process for recycling gypsum-based waste material into readily crushable members for use in the manufacture of cement and crushable members formed thereby |
US7105587B2 (en) * | 2001-03-07 | 2006-09-12 | Innovative Construction And Building Materials | Method and composition for polymer-reinforced composite cementitious construction material |
US6743830B2 (en) * | 2001-03-07 | 2004-06-01 | Innovative Construction And Building Materials | Construction board materials with engineered microstructures |
US6841232B2 (en) * | 2002-11-12 | 2005-01-11 | Innovative Construction And Building Materials | Reinforced wallboard |
US6902797B2 (en) * | 2002-11-12 | 2005-06-07 | Innovative Construction And Building Materials | Gypsum-based composite materials reinforced by cellulose ethers |
US7101426B2 (en) * | 2004-08-20 | 2006-09-05 | Innovative Construction And Building Materials, Llc | Inorganic matrix composite reinforced by ionically crosslinked polymer |
US20060054061A1 (en) * | 2004-09-13 | 2006-03-16 | Ruddick Douglas H | Bacteria and mold resistant wallboard |
DE102004051712B4 (en) * | 2004-10-23 | 2006-11-16 | Erlus Aktiengesellschaft | Process and geopolymer mortar for the production of supplementary shaped pieces on ceramic bodies |
US8574358B2 (en) * | 2005-12-06 | 2013-11-05 | James Hardie Technology Limited | Geopolymeric particles, fibers, shaped articles and methods of manufacture |
US20080075913A1 (en) * | 2006-09-26 | 2008-03-27 | Leonard Frenkil | Reinforced wallboard |
US8257486B2 (en) | 2008-03-26 | 2012-09-04 | Council Of Scientific & Industrial Research | Composition for building material and a process for the preparation thereof |
CN101544485B (en) * | 2009-04-20 | 2011-07-27 | 西安建筑科技大学 | Method for preparing geopolymer and organic macromolecule composite gelled material |
KR101031110B1 (en) * | 2010-08-16 | 2011-04-25 | 전창훈 | Synthetic wood made of a composition with improved antiseptic effect while increasing the texture of natural wood and a method of improving strength |
EP2589579B1 (en) * | 2011-11-02 | 2015-09-02 | Daw Se | Compound for treating plaster filled, removed or covered areas and their to treat plaster filled, removed or covered areas |
EP2868637A1 (en) | 2013-10-31 | 2015-05-06 | Construction Research & Technology GmbH | Geopolymer foam formulation |
US20150125683A1 (en) * | 2013-11-05 | 2015-05-07 | United States Gypsum Company | Gypsum products comprising silica gel |
US20190118160A1 (en) * | 2015-05-22 | 2019-04-25 | Alsitek Limited | Pollutant-reducing mineral polymers |
TWI600751B (en) * | 2017-02-23 | 2017-10-01 | Shi-Min Huang | Both heat and fire prevention of composite materials |
CA3055400A1 (en) * | 2017-03-06 | 2018-09-13 | Construction Research & Technology Gmbh | Inorganic foam based on geopolymers |
CN108947454B (en) * | 2018-08-06 | 2021-05-28 | 杭州余杭尖峰实业有限公司 | High-toughness inorganic mineral refractory layer and preparation method thereof |
US20210101832A1 (en) * | 2019-10-04 | 2021-04-08 | Premier Magnesia, Llc | Geopolymer cement |
CN112341139B (en) * | 2020-09-14 | 2022-01-28 | 中交第四公路工程局有限公司 | Soil curing agent and preparation method and application thereof |
CN114507057A (en) * | 2022-03-01 | 2022-05-17 | 江苏佳核新能源科技有限公司 | High fire-resistant low heat conduction composite material |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB591302A (en) * | 1945-05-04 | 1947-08-13 | James Bennie | Improvements in or relating to constructional materials |
US2531496A (en) * | 1949-11-04 | 1950-11-28 | Antioch College | Methods of forming a plaster mold or core for casting metals |
US3853571A (en) * | 1972-10-05 | 1974-12-10 | L Gelbman | Fire resistant composition containing gypsum and silicate-based material and processs for making same |
US4151000A (en) * | 1976-01-13 | 1979-04-24 | Produits Chimiques Ugine Kuhlmann | Anhydrite binder and method |
EP0032605A1 (en) * | 1980-01-18 | 1981-07-29 | Hewhand Limited | Pre-mix for forming a self-hardening composition, self-hardening composition and composite comprising the same, laminate and insulating structure made from the composite |
US4482379A (en) * | 1983-10-03 | 1984-11-13 | Hughes Tool Company | Cold set cement composition and method |
US5194091A (en) * | 1990-12-26 | 1993-03-16 | The Hera Corporation | Geopolymer-modified, gypsum-based construction materials |
-
1990
- 1990-12-26 US US07/635,735 patent/US5194091A/en not_active Expired - Fee Related
-
1993
- 1993-03-11 CA CA 2091491 patent/CA2091491A1/en not_active Abandoned
- 1993-03-11 EP EP19930301837 patent/EP0614858A1/en not_active Withdrawn
- 1993-07-05 CN CN93109898A patent/CN1097198A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US5194091A (en) | 1993-03-16 |
EP0614858A1 (en) | 1994-09-14 |
CN1097198A (en) | 1995-01-11 |
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