Document BvDgzdpnqdqb3JMKyrDdRQqvL
FILE NAME: Owens Illinois (OWILL)
DATE: 1951 Apr 3
DOC#: OWILL075
DOCUMENT DESCRIPTION: Patent - Calcium Silicate of Microcrystalline Lathlike Structure
Patented Apr. 3, 1951
; u J i. :vsr ;
: \j
2,547,127
UNITED STATES PATENT OFFICE
2,517,127
CALCIUM SILICATE OF MICJIOCRYSTALLINE LATIILIKE STRUCTURE
George L. K iiloiEsck. Toledo, Ohio, assignor to Owens-Illinois Glass Company, a corporation of Ohio
No Drawing. Application February 17,1949, -.'Serial No. 77,060
2 Claims. (CL 23-- 110)
l This invention relates to the production of a
2
be produced. These gels are formed a t tem pera
new integrated hydrous silicate .solid suitable for tures and during periods of induration used, for
use as insulation in th e field of high tem perature, example, in the m anufacture of sand-lim e brick
i. e., above 800 C.. a n d w hich m ay also be used and low density hydrous calcium silicate prod-
in th e low tem p eratu re field both as insulation 5 nets. Also, th ey have been founc^present along
and as a structural unit such as roof tile.
with calcium silicate hydrates in products pro
The prim ary object of this present invention duced at tem peratures in excess of those used
is th e production of a new hydrous silicate p rod in m an u factu rin g processes in th e siliceous field.
uct in which a pure m acrocrystalline structure A m ost typical example is the coexistence of these
is m atu red by reaction under h e a t and pressure. 10 "gels" an d a definite lath -lik e crystal stru ctu re
A fu rth e r object is th e production of a product in reaction m ixtures w here incom plete cry stal
wherein the crystals of this generated structure lization has occurred particularly in a lime-silica
are in random interlocked dispersion throughout slurry in which the lime content is greater th a n
the product, thus providing a high degree of th a t commonly employed, and which has been
stre n g th not found in th e usual hydrous silicate 15 indurated a t certain controlled am i regulated low
products.
tem peratures. However, by indurating a t pres
A nother object is th e production of a new sures in excess of 125 pounds per square inch
hydrous silicate h a v in g .th e properties of great f125 p. s. i.) and 173 C. these "gel" phases may
resistance to high tem p eratu re as well as re sist be completely avoided, and they may also be
ance to high therm al shock.
avoided - by indurating fo* long periods a t low
A still fu rth e r object is to produce such a p rod pressures.
uct w ith high resistance to CO:- attack: of air and
T he essence of this present invention is the
resistance to corrosion by water.
preparation, of a synthetic, integrated hydrous
O th er objects will be a p p a re n t from th e fol silicate product having a m icrocrystalline la th -
lowing. (IcseHpUve m atter.
iXi like .structural form ation, interspersed with
Tin* present im vni.ien provides an integrated
voids, which may be prepared in integrated form
m aterial consisting basically c?i' a reaction p rod uct of. lime and silica in th e fo ur of a hydrous
caicium silicate having the formula
through a range of apparent densities at tem peratures considerably lower ami in time periods much shorter, th an have heretofore been consid--
5Ca0.5Si0:r.H::0
:;o cred feasible. By control of variables, such as temperatures,
Structurally the.m aterial comprises such silicate pressures, time of induration, degree of disper
in the form of microscopic lalh-fikc crystals in sion of the solids in liquid carriers, the degree of
terspersed with microscopic voids, the m aterial fineness of the solids, any and all deleterious gels
being of light weight, having a microscopically ;i5 or gel-like phases m ay be substantially elim i
fine texture and visually being of apparent homo- nated and pure lath-like microcrysfalline crystals
acuity throughout the body of the m aterial. It varying in length from the submicroscopic to
combines light weight and a texture giving h
lengths easily discernible under a microscope will
a high insulating value, w ith a modulus of ru p * be the final resultant.
tu re ad apting th e m aterial for various insulating 40 This m icrocrystalline la th structure is superior
and structural purposes as more fully pointed cut to other hydrous silicate type structures in prop
h c e in a ite r.
erties such as heat insulation, modulus of run-
It w eh-know n m rh nrHi of hydrous smctH t uve, shrinkage during drying and stability a t ele
products th a t reactan ts such ns silica and w ater vated tem peratures. This new product is supg-
r e a d under luvu nod. or prw-s-u-c to burn gels or ir> rior to previously m anufactured hydrous silicate
' el-hke riicrocrystalllne structures, and th a t the products w ith respect to its resistance to CO2 a t
exten t to which they ar> converted to crystailin ' ta c k of air and resistance to corrosion by w ater.
solids depends cn their nature, the tem perature
It can be synthesized from high calcium quick
employed, the time of induration mi* the com lime. or high calcium hydrated lime, and ground
position of th e m ixture from w hich they are to 50 quartz or various o ther form s of silica w ithout
2,547,127
3 the addition of any bonding m aterial such as
4
indurated mass will always leave a volume of
asbestos, blast furnace slag, P ortland cement, voids '*re:\ter th an the volume of the lath crystals.
plaster of Paris, bentonite, etc.. commonly used
In th e'h eav ier den'.sltv m aterials, i. e., those in
in hydrous 'silicate p ro d u c t' for providing !ke ran vlu-re an agent feu* retarding th
stre n g th and thus may be produced a t com para- g sell line; of fhe solids is unnecessary, the compo
lively low cost.
nent lime n u l perforin the function of m aintain-
The resultant product to be produced through
in;; Uhi s.did ; in proper dispersion and will pre-
tins invention is a true crystalline solid th a t will veut any harm ful .segregation thereof.
possess the advantages of such; namely, freedom
To malie H o desired light density product, the
from shrinkage and cracking and w herein no v 10 slurry should be prepared in a CaO/SiOs m olar inforcem ent, such as asbestos fiber, need be u!s- rat io of ap>wrp;hnnivby 1.0 by mixing first the
li/.cd for increasing stren g th or preventin' crack- lime and h o t w ater and then adding quartz. De
in!'; in th e finished product. T ins crystalline sol id is to bo produced through
pending upon Urn a p p aren t density required, an am ount of vaUirdin ' agent such as asbestos or
an extrem ely wide range of a p p a re n t densities j- starch will bo added sufficient to prevent segre
hsving practical application and usefulness from
gation of the su'kis for a predeterm ined time in
the lightest through Lire range of heavier a p feri al prior to initiation of reaction.
p a re n t deaxitie to th e ex ten t necessary in miy
The slurry will be poured into pans or molds
practical commercial application.
Imving a dcshied pr*'betermined shape, the molds
Experience has shown th a t in the productwm ^ placca in an indurai nr where pressure and heat
of this purr crystalline solid, two m ethods m ust wid bo applied io bring about, under reaction,
be practiced in order to. cover th e full range "f a p p a re n t densities, i. c,. from th e extrem e lower
hc form ai ion of iho mv.rom\vsi:>lUno lath stru c ture .nd the complete inU ration and drying of
density up to approxim ately 15 pounds per
Iho product, 'flic drying of the product m ay be
cubic foot 1 15*' p. c. f . ) . T hroughout th is range g. iuvcm plishcd in th e indurato!* or in the usual
of lower densities relatively great quantities of dryiug oven.
w ater are required, an d it is necessary to utilise
In the heavier densities the same process is
an agent of retard atio n to prevent setFing of the employed excepting only th a t no retarding agent
solids in the slurry form ulation and to 'm aintain need be utilized. Kcgardless of the density de
proper dispersion thereof in the aqueous m edium . -,0 sired in h'*- u ltim ate product, tjjp mole ratio of
In the density range upw ards from approxi lime io viiiwu in the Murries, should be approxi
m ately lb -' p. c. f.. the com ponent solid m atetails of the slurry will' m ain tain th eir own props*
m ately 1.0. The tem perature, pressure, and time utilized
dispersion in the aqueous medium for a period at induration v. i.-i determ ine the extent to which
of time sufficient to perm it initial reaction to cc- ..;i the in h eren t -.els are elim inated and th e per
o r to iree:-.c o; aiaesi any possible separation or versarne o- pave* mierocryst-alline solid obtained.
segregation of lh r com ponents.
For example, iho tem perature and pressures
In the light ap p aren t density ranee, it may ho ustuuly utilized in the lime-silica systems will, in
foetid necessary to add to the m ixture of lime, [\ period of about 15 hours, .provide incomplete
MUfu and wai-.T an anm im t of highly spicalated /(J vry. U'.llizuUun of Hi. com ponents of this present
;isbesios. or oiiuT H'lrardinu agent, sufficient ;o r.iurry but m en though the reaction may be in
sa; -;ort the : ra a u la r com ponents in a fine dis complete with some gel phase rem aining, yet a
persion for a period of tim e sufficient to perm it '.veal portion o; Hie solid stru ctu re will reach the
m unition of a cel phase which.will th e re a fter re- si age of a m ioivyrystaliine lath stru ctu re inter-
m \ ; sodas ffi their proper dispersion.
45 s noised with v l d s and having appreciable
I t is intended th a t alm ost any agent ihr-.t will stren g th as weii a s'm a n y other desirable physi
ineivuso the viscosity of the slurry in relatively cal properties.
-'hurt, time 10 prevent segregation of the solid
The reacted product so obtained contains too
mav '(.
as the reigrding ;ew*nt providing it
;(M i h ve?contage of gei or gel-like m icrocrys-
does not have a deleterious effect upon the
r,o tvddno so lids winch results in a product th a t
m an he.,.red product. O ther m a id in g agents cracks upon drying.
. uch e.s highly pulped and beaten paper, starch
By m dnraa mese lime-silica slurries a t
- = ' anil .v a,.: m s may h" utilized as the re ta rd a n t pressures and. tem peratures well, beyond the
she am-esss formulation.
(sum cuvnbtions. particularly slurries of cqui-
W hen the finely divided solid ea rp o n e n ls of .-.5 ino.'ar r.-uwo of the lime and silica, practically all
iiu- sio:t \- fernudaiion. nam ely. lime and silica
cl nuT-mi'on is m im inated w ithin a very few
are dispersed th r o w n sr very iar.'T v o h sT ' of
hours, and 11 t.n diying. th e aqueous m edium is
eh r v ; h he ce.-pponenis uj- aoli-Uou r e - dissipai od. 'cavili.*: m its place a volume of voids
1: cd in vide sta te oi dispersion through the of ,aiorosf*o*nc o im ersio n c r less and w ith said
use of a retard in g ag en t and the row : ion carried w V: .;s being m excess of the volume of the re-
to hydrated calcium silicate. Hie .idh my.-dab;
p m*c w'whiKine lath structure.
ca .p u re ; s ; aicium shivai? will be induced to
The
of the slurries to be used will be
'rev and present a random ly disjMvrod m ass of
V swab-v by ,sw e.-irea ap p aren t density of
huh m-'wivs throughout the uUir* volume in
ho iudurm isi ] racuut. For tlm lower densities.
which the r c 'elivc agents have been h Id in ms- 05 10 the ranee <T about 5 to 15 n. c. f.. a suspen-
m -sion praw :..o end during at; least a portion of
aid siiC-li as any of the aforem entioned
the reaction period.
a .onls a ill ' s' m troducvd into a m ixture of
Moroni or. in the course of their crystal growth
i'l-eHuv h.vuiau d Mme and silica in which the
the tormina .lath crystals of the various clusters
m olar rad o of Hie Cat) to th a t of the S1O2 is ap-
'.hero h whl lo a e n sid e rd b e (eurcr 'cross Id yo < xim:.' n. Li), h'he quicklime is hydrated com-
varying points of contact with each older to thus
, lt .. .v so 1 ... id y by ndding it to hot w ater
uiteriace and interlock inu ;l n rrm sn o n t U iivr-
, 1 -fi-dVr. F > sud Mirriti continuously and
ffinu.u donah nitv.ork 01 m ierocrystalliiie lath
-, i:-a..::'Tv tin* soiling m ixture for 1 or 2 m in
.sLrr.i:i..rc in random dispersion.
cies. T;a.* wmouru, of water, in p arts per p a rt of
The .'.usripauon oi the excess waior from the v5 dry g-.oibU, a h i -range from about 10 for the 5
' ^ -O v)
h : -L i x L L
2,547,127
5
6
p. c. f. a p p a re n t density product to about 4.5 for shaping, cutting and sawing as well as th e polish
the 15 p. c. f. a p p a re n t density product. The
ing of its surfaces to very smooth finish.
am ount of re ta rd a n t utilized will vary according
From the preceding, it should be apparent th a t
to its physical ch aracteristics from about 10 p er this new product, nam ely, this pure microcrys-
cent by w eight of th e solids for the lightest a p 5 tallin e la th stru c tu re has physical properties s u
p aren t density to ab o u t i percent for th e 15 p. c. f. perior to previously known hydrous silica p ro d
apparent density.
ucts.
In th e range from about 15 to 125 p. c. I. a p
In order to render a complete understanding
parent density the m olar ratio of lime to silica of the product, its form ation and characteriswill be 1.0:1.0 and (w ater in p a rts per p a rt of dry 10 tics a n d in p a rtic u la r th e invention herein con
solids from about 4.5 to i.5>.. T he freshly h y tem plated, th e following description is set forth.
d rated lime alone will suffice to prevent differen
The form ation of this pure microcrystalline
tial segregation of th e solids. I n the range from la th stru ctu re is actually a tran sitio n of the com
about 25 to 45 p. c. f. a p p a re n t density <the ratio ponent m aterials; lime quarts and w ater, from
of w ater to solids will range from about 1.5 to .75 15 th e solid or solution, first to a true gel fo rm a
parts w ater for each p art of dry solids). In this tion, thence to an extremely fine crystalline struc
range; an equivalent am ount of. dry powdered
tu re b u t still retaining th e properties of a gel,
C a (O H h instead of quicklime will be used, and th en to a com bination of this last .mentioned gel
for products in excess of 45 p. c. f.t th e raw mix an d crystals of lath -lik e stru ctu re in form ed clus-
will be a plastic paste. Such pastes will be h a n 20 ters, to a conversion of the whole to a pure m icro
dled or formed in a m anner sim ilar to th a t for crystalline lath structure in formed clusters in
handling elax mixes for brick or tile, th a t is, they
random dispersion through the mass with ap
may be hand placed, poured into molds or ex proximately complete elim ination of any gel for
truded.
mation, with the complete dissipation upon dry-
As a n indication of th e strength obtainable in 25 ing of all uncom bined w ater and the form ation
this new product, w ithout asbestos, as well as the thereby of voids in aggregate volume in excess of
sh o rt in d uratin g periods required, th ere is listed th e aggregate volume of the lath-like crystals,
here below a table showing the results obtained
the lath crystals being of parallel extinction, posi
with two sam ples'in three periods of induration
tive elongation, having indices of refraction:
a t a tem p eratu re an d pressure of approxim ately 30 A lpha--i.5830.003; gumma^--1.5940.003, th e
208 C., and 250# respectively.
lime, silica and water being present in the crystals
in the m olar proportions of 5, 5, 1, respectively;
Table 1
this transition for practical and commercial pur
poses being effected through the application of
! I I *!i I'1-. [ t i f i l i ! . U Oil
12 35 pressures and tem peratures which will vary with
the degree of comminution of the solid m aterials
M f'.ju iiJ : n f n r t > ! i w r , f>. s. ` S.'lJjipli* ) '
illlil-;; <! 11j [ t| f: ', I-. s . i i i U i p 2 I h -t is il y , ]>. r f. I ' 11!11!11I I
: 1v, [i.c. f >'V.ini'i.' 1 ' ... >1 'I'! m:.I l\ I
i'.' l l . !,<*>>, p e r r e n i V r r r K . T .......................
2"1 212 employed and the time in which it is desired to
. 277 211 '20. 7 21. 1 10. 0
complete the transition to an integrated and dried
21. 4 10. r. 20. O product.
O O 1! S
(>.r. ! . y
.y /.fi
40
The term "unity" as used herein shall he inter
preted as m eaning a mole ratio of 1; 1. in the cry s
1 Averru:'* two r e s u l t s .
tals of the finished product. Modifications may be resorted to within the
From Table #1, it is apparent th a t the average spirit and scope of my invention.
modulus is 238# p. s. i. w hich is above th a t found 45 I claim :
**
in the usual hydrous silicate products.
1. A shaped product com prising a porous body
In addition to th e above factors, it is found stru ctu re consisting essentially of pure, sy n th e
th a t in the field of compressive strengths this new sized crystals having th e form ula
product is again superior in its field, as 20# den sity will have a compressive strength of 500# p. s. i.. 20# density. 900# p. s. i., an d 45.5# d en sity, 2350# p. s. i.
The lath-like microcrystallinc structure ob tained thro u g h this invention is of g reat value as
0A
5CaO .5siO 2.H 2O
ana being continuously integrated with each
other without any other bonding medium, and
forming a three-dimensional network inter
spersed w ith voids, the aggregate volume of the
insulation in the high tem perature field and tests 55 voids being in excess of th a t of the crystals.
to determ ine its applicability indicate it will w ith
2. T he m ethod of form ing an integrated pro d
sta n d excessively high tem peratures for long pe uct wrhich com prises form ing an intim ate reactive
riods of tim e w ithout breaking or disintegrating. m ixture consisting essentially of lime, silica, and
F or exam ple, th is m aterial at 20TM density, was w ater, th e am ount of w ater in the m ixture being
subjected to a series of te-*ts wherein th e surface fi0 w ithin th e range of about 4.5 to .75 times the ag
tem perature, from direct flame application, gregate weight of the solids, the m olar ratio of the
reached approxim ately 2000' F. an d a fte r two reactive CaO a n d S1O2 being approxim ately 1:1,
hours of exposure thereto was subjected to a shaping the mixture, subjecting the shaped m ix-
stream of cold w ater under pressure w ithout j;- tu re to a predeterm ined indurating tem perature
sh a tte rin g an d w ith only superficial surface and pressure in excess of 173 C. and 125 p. s. i..
cracking. . T h e sh rinkage of this m aterial is extrem ely low
respectively, an d thereby causing a reaction by
when compared to other lime-silica products and
Which th e lim e , s ilic a a n d w a te r a r e c o n v e r te d
its hard n ess of 0.5 according to Mohs scale, to com pletely to a n in teg rated porous stru ctu re of
gether with its quality of with-funding extreme 70 pure m icrocrystalline lath crystals, having the
th erm al shock upon quenching makes it a most form ula 5CaO.5siO 2.H2O. said crystals being in
desirable product for m any purpose; and in p a r random dispersion and being integrated with
ticular for fire resistant structures. Such a prod each other and thereby maintaining said struc
uct. because of its rigid structure lends itself to ture in integrated form independently of any
various form s o r m ethods of finishing, such as; 75 o th e r bonding medium , an d drying the product to
2,647,127
7
remove free water and leave a product in which
8
FOREIGN PATENTS
the crystals have the formula 5Ca0.5Si0s.H20. GEORGE L. KALOUSEK.
Number 2,128
Country
Date
G reat B r ita in ___________ of 1909
REFERENCES CITED
O 501,024 G reat B r ita in _____ Feb. 20. 1939
T he following references are of record in the
OTHER REFERENCES
file of this patent:
. D ana: Textbook of Mineralogy. 4th ed., re
UNITED STATES PATENTS
Number
Name
Date
vised, New York. New York. John Wiley and 10 Sons, 1932. page 641.
2,215,891 T h o m p so n................. Sept. 24, 1940
2,421,721 Sm ith ___________
J u n e 3,1947
2,469,379 F r a s e r -------------------- May 10. 1949