CA1247659A - Nickel ion-free blue glass composition - Google Patents

Abstract

Abstract A blue glass composition is disclosed. This blue glass composition is based on a standard formulation for soda/lime silica glass, except that neither the basic glass composition nor the coloring components therefor contain nickel, The blue glass color is developed by using coloring components consisting essentially of 0.3-0.6% Fe2O3, 0.004-0.008% CO3O4, and 0.0001-0.001%Se.

Description

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NICREL ION-~REE BZ,UE GLASS CO~pOSITION

Thl~ applicatlon is directed to a yla88 composition which has a blue body color. The gla88 compo~ition i~ nicke1 ion-free, which allow~ on~ to temper such a compo~ition without wocrying about breaking the glass at sites where nickel stone3 exi~t.

G1a3s compositiona havlng various body color~
are used by architects in glazing buildings. Normally, the color selected by the architec~ is one whlch serve~
two functions. A first function is that the glass wilr be asthetically pleasing when viewed from the exterior of the bullding. A second function of the glass is tbat it works to reduce ~ha amount o h~at ab~orb0d ~rom ~ha exterior of the building to the lnterior of the building so that th~ alr conditionlng load in tha buildlng is reduced.
In most ca~es the large spandrels oP glass used in making windows for such bui1dlngs have to be tempered. Such ~pandrels are tempered 80 that in ca~a they are acciden~ally bcoken they will sh~tter lnto small, blunt p~ece~ of glas~ which will not harm anyone.
If the glass i8 not tempered, ~he glas~ may break into long, thin pieces of gla~ which might cause lnjury.
If glass contains nickel in it~ compo~ition, the nickel ha~ a t~nd~ncy to react with ~ulfur in the 91a88 to form nickel ~ulfide. The nickel sulfide settle~ out in the gla~s as a d~fect known as a stone. A stone is a tiny sand-like imperfection in the glas~. When such glass containing ~tone~ is heated to an elevated temperature and rapidly cooled thereProm to temper the same, the ~r~s concentra~ion about area~ of stones is very, very high. As a re3ult, in many Ca88S~ a ~tone . . .

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wlll cau3e concentration ~tre.~ses which result in a rup~ure of the glas~ during lt~ tempering. Of cour~e, if the gla~s ruptuees during temp~rlng, the glasa ~pandrel i~ destroyed and all of the money spant on producing the S ~pandrel to that point i8 lo~t.
In addltion to breaking during temperingt nickel sulfide stona~, when ~mall~r than a certaln 8ize, can pass tempering undetected without causing any damage.
How~ver, som~ of these small ~tonea that are formed at 10 high temperature will undergo, through phase tran~formation, a low temperature phase change when the ~la89 $8 cooled ~o room ~emperature. The tran~ltion of nickel ~ulfide from high to low temperature formQ is usually accompanled by a volume expansion of 2 to 4~. -lS Thi-~ increa~e in volume would initiate microcracks in the gla~ which can lead to spontaneous fracture of ~he tempeeed glassi. This phase transformation i3 a slow proces~ ~nd can take months or y~ars d~pending on the ~ize o th~ ~tone and it~ location in the glass.
The present invention is directed to the provision of a glass composition having a blue body color which is nlckel ~ree. ~y making the gla~s n1ck~1 fr~e, we eliminat~ the formatlon of nickel sulfide 3tones in the glass and the later diffioulty occa3ioned by stresY
25 concentrations about the stones when the glass is rapidly cooled to room temperature, No search was conducted on ~he subject matter of this invention disclosure in the U.S. Patent and Trademark Office or in any other earch facility.
30 However, we are aware of two U.5. patents which are of interest herein. The~e two patents ar~ U.S. patent

2,938,808, isQued May 31, 1960, for ~Gla~s Composition.~
This patent was ~ubsequently rei8~ued a~ Re.~5,312. Also of intere~t i~ V.S. patent 3~723,142, issued March 27, 35 1973, for ~Neutral Gray Gla~s.

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U.S. patent 2,938,808 di~clo~es as a new article of manufacture a neutral color sheet of ylas~ having a thickness in a ranye of 1/8-1/4 inch. The glas.s is suitable for glazing purposes and substantially uniform transmission of light in ~he proportion of the spectrum line between 440 and 660 millimicrons, an excitation purity of below 7%, a total solar energy transmittance between 40-48%, and a total luminous transmittance between 35-45%. The glass composition disclosed in this patent consists essentially of base ingredients in percent by weight as follows: 60-75~ SiO2, 11-20%
Na2O, 0-10% K2O, the sum of the Na2O and the K2O
being 11~21%, 6~16~ CaO, and 0-10% MgO, the sum of the CaO and MgO being 6-18%, together with 0.4% Fe2O3, 0.0076-0.008~ Co3O4, 0.009-0.126% Nio, and 0.005-0.0056 Se at 1/4 inch thickness. The patent teaches that the amount of the colorants Fe2O3, Co3O4, NiO and Se being greater as the thickness of the sheet is less than 1/4 inch and being approximately twice the above listed amounts for each colorant when the thickness of the sheet is 1/8 inch.
U,S. patent 3,723,142 discloses a neutral gray colored heat absorbing glass having a low excitation purity. The glass is defined as consisting essentially 25 Of the following base components in percent by weight-68-75% sio2, 0-5% A12O3, 5-15% CaO, 0-10% MgO
[6-15~ CaO~MgO], 10-18% Na2O, 0-5% K2O [10-20~
Na2O+K2O] together with coloring components of 0.1-0.5% Fe2O3, 0.003-0.02~ Co3O~, 0.0005-0.001%
3Q Se, and negligible NiO. The specification o~ the patent states that the quantity of NiO should be less than about 0.002% and preferably less than 0.0004~.

This invention i8 directed to blue gla~
composition, In partlcular, thiA inventlon is dlrected to a blue glass compo~i~ion having no nickel ion contalned therein.
In accordance with the present invention, a blue glass composition having no nickel ion contained therein consists essentially of the following base component~ in percent by weight: 68-75~ SiO2, 0-5%
A1~03, 5-15~ CaO, 0-10~ MgO, 10 18~ Na2O, 0-5~
K~O, where CaO+MgO i8 6-15~ and Na2O+K2O i~ 10-204 together with coloring components of 0.3-0.6% Fe2O3, 0.004-0.008S Co3O4, and 0.0001-0.001 Se.

The novel features that are considered characteri~tic of the invention are set forth with particularity in the appended claim~. The invention itself, however, both as to lt8 organi~ation and it~
method of operation, together with additional advantageR thereof, will best be understood from the following de~cription of ~pecific embodiments.
The following de~cription i~ what we con3ider to be a preferred embodiment of the blue glass composition of our invention, The following de~cription also sets forth what we now contemplate to be the bes~ mode of making the blue gla~s compo~ition of our lnvention. The de~cription i~ not inte~ded to be a limltation upon the broader pr~nclpla~ of thi~ inventlon.
This invention i~ direc~ed to a blue body-colored automotive and architectural tinted glas~.
The glas~ composition i8 nickel-free ~o that nlckel ion 30 i3 not available to react with ~ulfur to Eorm nickel sulfide ~tone~ in the glass which may result in a spontaneous br~aking and ~hattering of the tempered gla~, The gla98 compo~ltion which is colored i a basic J

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soda/lime silica qlass. The basic material~ used in making up the composition are as follows: 68-75% SiO2, 0-5% A12O3, 5-15% CaO, 0-10% MgO, 6-15~ CaO~MgO, 10-18~ Na2O~ 0-5% K2O, and 10-20~ Na2O~K2O.
In accordance with a preferred embodiment of our invention, coloring components were added to the basic composition. Neither the coloring components nor the basic composition contained any nickel ion. The coloring components added included 50 ppm cobalt, 3 ppm selenium (Se) and 0.42 wt~ % iron oxide (Fe2O3). When these colorants were mixed and melted with the basic glass composition, the following measurements were obtained using illuminate ~C~ and corrected to 0.25 inch glass thickness transmission (T) equaled 54% ~ 1%. The dominant wavelength was 482nm + lnm. The purity of the color was 13% ~ 1~. The target color coordinates for this glass were X = 0.2799 and Y = 0.2947.
In accordance with the broad teachings of the blue glass composition of our invention, the colorant elements may have the following limits: Fe2O3 may vary from 0.3 to 0.6 wt. %; cobalt oxide may vary from 0.004 to 0.008 wt. ~, the selenium may vary from 0.0001 to 0.001 wt. ~. The major factor in this composition, however, is the fact that there is no nickel present. In - 25 the absence of nickel, the coloring elements still give a very desirable blue body color to the glass composition.
While particular embodiments of the novel blue glass composition of our invention have been illustrated and described, it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the invention. It is intended to cover in the appended claims all such modification~ and equivalents as fall within the true spirit and scope of this invention.

Claims (2)

The embodiments of the 6 invention in which an exclusive property or privilege is claimed are defined as follows:

1. A blue glass composition having no nickel ion contained therein and consisting essentially of the following base components in percent by weight: 68-75%
SiO2, 0-5% A12O3, 5-15% CaO, 0-10% MgO, 10-18%
Na2O, 0-5% K2O, where CaO+MgO is 6-15% and Na2O+K2O is 10-20%, together with coloring components of 0.3-0.6% Fe2O3, 0.004-0.008% CO304, and 0.0001-0.001%Se.
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2. The blue glass composition of Claim 1, wherein the coloring components are 0.42% by weight Fe2O3, 0.005% Co3O4, and 0.0003%Se.