Abstract:
Compositions of matter that are antifreeze composition, coolants, heat transfer fluids, and de-icing fluids based on the use of coalescent efficient glycol ethers.

Description:
[0001]    This application is a utility application based on U.S. Provisional patent application Ser. No. 62/279,073, filed Jan. 15, 2016, from which priority is claimed. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    This invention deals with compositions of matter that are antifreeze compositions, coolants, heat transfer fluids, and de-icing fluids. For purposes of discussion in this specification, all of the afore-mentioned materials are referred-to as “antifreeze” compositions. 
         [0003]    NFPA 13, Standard for the Installation of Sprinkler Systems, has included guidance on the use of antifreeze compositions in fire sprinkler systems. Antifreeze compositions may be used in fire sprinkler systems where the piping system, or portions of the piping system, may be subjected to freezing temperatures. 
         [0004]    The term “antifreeze” refers to a composition which reduces the freezing point of an aqueous solution, or is an aqueous solution with a reduced freezing point with respect to water, for example, a composition comprising a freezing point depressant. 
         [0005]    The term “coolant” refers to a category or liquid antifreeze compositions which have properties that allow an engine to function effectively without freezing, boiling, or corrosion. The performance of an engine coolant must meet or exceed standards set by the American Society for Testing and Materials (ASTM) and the Society of Automotive Engineers (SAE). 
         [0006]    The term “heat transfer fluid” refers to a fluid which flows through a system in order to prevent it from overheating and transferring the heat produced within the system to other systems or devices that can utilize or dissipate the heat. 
         [0007]    The term “de-icing fluid” refers to a fluid which makes or keeps a system, a device, or a part of a device free of ice, or a fluid that melts ice. 
         [0008]    The term “ultra-pure water” as used herein refers to the water obtained by the process as set forth in U.S. patent Publication 2010/0209360, published Aug. 19, 2010 entitled “Method for making a Gas from an Aqueous Fluid, Product of the Method and Apparatus Therefor. 
         [0009]    The term “non-flammable” as used herein refers to the standard for flammability set forth in UL Test Standard 2901. 
         [0010]    “Coalescence” for purposes of this invention means similar or like properties as a group. 
         [0011]    These compositions (hereinafter “antifreeze compositions”) have multiple uses, as they can be used to prevent freezing of certain systems, but can also be used as additives for certain applications in which heat control is an issue. 
         [0012]    It is known to use antifreeze compositions in heat exchanger systems, de-icing applications, for example, on airplane wings and fuselage, radiators in automobiles, automobile and truck batteries and other vehicles, such as armored tanks, and the like. 
         [0013]    Currently the only antifreeze which is approved for use in CPVC fore sprinkler piping by NFPA 13 is glycerin. Ethylene glycol and propylene glycol have been used for hard piped sprinkler systems. All of these antifreeze materials are flammable. Flammability and a variety of other issues have created a need for a non-flammable antifreeze materials for sprinkler piping. A variety of “compounds” and additives have been evaluated in the prior art without any success. 
         [0014]    In such applications, the antifreeze composition must be contained, and the materials of the containment system must come in contact with the antifreeze compositions. Such systems are manufactured from metals, alloys of metals and other components forming the different parts of the systems. 
         [0015]    Thus, one of the major issues in using antifreeze compositions is the prevention of corrosion in such materials. Another issue is flammability of the antifreeze compositions, especially when such antifreeze compositions are used in fire sprinkler systems. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0016]      FIG. 1A  is a graph showing conductivity end freezing points of aqueous solutions without potassium formate.  FIG. 1B  is a graph of various properties of aqueous solutions without potassium formate. 
           [0017]      FIG. 1C  is a graph of conductivity and freezing point of aqueous solutions with potassium formate. 
           [0018]      FIG. 1D  is a graph of various properties of aqueous solutions with potassium formate. 
           [0019]      FIG. 1E  is a graph of freezing point comparison with and without potassium formate. 
           [0020]      FIG. 2A  is a comparison of samples  130 ,  131 , and  132 , initial properties compared to commercial antifreeze. 
           [0021]      FIG. 2B  is a comparison of sample  130 ,  131 , and  132 , at 30 days at high ambient temperature stability 70° C. for 30 days. 
           [0022]      FIG. 2C  is a comparison of sample  130 ,  131 , and  132 , at 90 days at high ambient temperature stability 70° C. for 90 days. 
           [0023]      FIG. 2D  is a comparison of sample  130 ,  131 , and  132 , at 40 cycles high ambient temperature stability 66° C. 
           [0024]      FIG. 3A  is a graph of corrosion rate at 30 days. 
           [0025]      FIG. 3B  is a graph of weight loss rate at 30 days. 
           [0026]      FIG. 3C  is a graph of corrosion rate for 60 days. 
           [0027]      FIG. 3D  is a graph of weight loss for 60 days. 
           [0028]      FIG. 3E  is a graph of corrosion for 90 days. 
           [0029]      FIG. 3F  is a graph of weight loss for 90 days. 
           [0030]      FIG. 4A  is a table showing corrosion rate and weight loss data at 30 days 
           [0031]      FIG. 4B  is a table showing corrosion rate and weight loss date at 60 days 
           [0032]      FIG. 4C  is a table showing corrosion rate weight loss data at  90  days 
           [0033]      FIG. 5A  is a graph showing % volume changes for formulation  130  and various rubbers and plastics. 
           [0034]      FIG. 5B  is a graph showing % weight change for formulation  130  and various rubbers and plastics. 
           [0035]      FIG. 5C  is a graph showing % volume change for formulation  131  and various rubbers and plastics. 
           [0036]      FIG. 5D  is a graph showing % weight change for formulation  131  and various rubbers and plastics. 
           [0037]      FIG. 5E  is a graph showing % volume change for formulation  132  and various rubbers and plastics. 
           [0038]      FIG. 5F  is a graph showing % weight change for formulation  132  and various rubbers and plastics. 
           [0039]      FIG. 6A  is a table showing data for formulation  130  and various rubbers and plastics. 
           [0040]      FIG. 6B  is a table showing data for formulation  131  and various rubbers and plastics. 
           [0041]      FIG. 6C  is a table showing data for formulation  132  and various rubbers and plastics. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0042]    It has now been discovered that antifreeze compositions can be formulated that are essentially low cost, non-flammable, have very low freezing points, and are essentially non-corrosive to metal components of systems used for handling such antifreeze compositions. 
         [0043]    What is disclosed herein are non-flammable antifreeze compositions comprising the incipient materials, water; a coalescent efficient glycol ether selected from a group of materials having the general formula: 
         [0000]      RO(CH 2 CH 2 O) y R′ or,
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0044]    In the first formula, RO is selected from a group consisting of an alkoxy group of 1 to 6 carbon atoms or phenoxy; R′ is H, or —C(O)CH 3 , and  y  has a value of 1 to 6. In the second formula, RO is an alkoxy group of 1 to 4 carbon atoms, the phenoxy group or acetoxy group; is R′ or —C (O)CH 3 , and  y  has a value of 1 to 3, wherein the boiling point of the coalescent efficient glycol ether is 190° C. or greater at 760 mm Hg. 
         [0045]    A third component is a non-flammable compound selected from the group consisting of sodium formate, potassium formate, lithium formate, rubidium formate, cesium formate, beryllium formate, magnesium formate, calcium formate, strontium formate, barium formate, and mixtures of these components. 
         [0046]    In addition, it is contemplated within the scope of this invention to use one or more additional adjuvants and materials in the formulation. Such materials comprise such materials as waxes, silicate stabilizers, thickeners, dyes, and the like. It is also contemplated within the scope of this invention to use mixtures of these materials with the basic formulation. 
         [0047]    Another embodiment is the use of the basic formula set forth Supra in conjunction with other sources of carbinol, such as sugar, glycerin, polyethylene glycol, polypropylene glycol, diethylene glycol, and, salts such as sodium chloride and sea salt. Also contemplated within the scope of this invention are mixtures of these materials. 
       DETAILED DESCRIPTION OF THE DISCLOSURE 
       [0048]    Thus what is disclosed and claimed herein are non-flammable antifreeze compositions based on water. the amount of each of the components here is based on the total weight of the components, and the amount of water that can be used herein is 0.1 to 95% weight percent. A preferred amount of water is from about 15 weight percent to about 75 weight percent and the most preferred embodiments is water at 40 weight percent to 65 weight percent. 
         [0049]    A second component of the antifreeze composition is a group of materials that are coalescent efficient glycol ethers having the general formula RO(CH 2 CH 2 O) y R′ or, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein in the first formula, RO is selected from a group consisting of an alkoxy group of 1 to 6 carbon atoms or phenoxy; R′ is H, or —C(O)CH 3 , and  y  has a value of 1 to 6, and in the second formula, RO is an alkoxy group of 1 to 4 carbon atoms, the phenoxy group or acetoxy group; R′ is H or —C(O)CH 3 , and  y  has a value of 1 to 3. 
         [0050]    These materials can be used singularly or combined in two or more combinations. They are used in this composition at from 0.1 to 85 weight percent, based on the total weight of the composition. Preferred is from 20 to 60 weight percent and most preferred is from 40 to 55 weight percent based on the total weight of the final composition. 
         [0051]    A third component of the antifreeze composition is a non-flammable compound selected from group consisting of sodium formate, rubidium formate, cesium formate, beryllium formate, magnesium formate, calcium formate, strontium formate, barium formate, potassium formate, lithium formate, and, mixtures of these compounds. These compositions are used in the antifreeze compositions at from 0.1 to 85 weight percent of the total composition. Preferred is a weight of from 0.1 weight percent to 70 weight percent and most preferred is the use at 0.1 to 50 weight percent based on the weight of the final composition. 
         [0052]    In addition, it is contemplated within the scope of this invention to use corrosion inhibitors, such as, for example, sodium silicate, potassium silicate, and sodium trihydroxysilylpropyl methylphosphonate. The corrosion inhibitors are used at 0.1 to 10 weight percent based on the weight of the total composition. Preferred is from about 3 percent to about 8 percent and most preferred is from about 5 percent to 7 percent by weight based on the total weight of the final composition. 
         [0053]    Other adjuvants include waxes, such as carnauba, paraffin, polyethylene wax or polypropylene wax, PTFE, microcrystalline waxes and blends of waxes which are used primarily at about 0.2 weight percent to about 10.0 weight percent based on the total weight of the final composition. Such waxes can be obtained from a variety of commercial sources such as Michelman, INC. Cincinnati, Ohio. 
         [0054]    In addition, there can be used thickeners or rheology modifiers, for example for use on de-iceing airplanes wings. Any conventional thickener can be used. Cellulosics such as CMC, HMC, HPMC, and others, that are chemically substituted cellulose macromolecules, polyvinyl alcohol, metal oxides such as silica, clays: attapulgite which also disperses suspensions, bentonite (both flocculating and non-flocculating), and other montmorillonite clays. Preferred for this invention is carboxymethylcellulose which is used primarily at about 0.2 weight percent to about 5.0 weight percent based on the total weight of the final composition. 
         [0055]    As indicated Supra, ultra-pure water can be used in this invention and it can be used is conjunction with other water, such as well water, city water, river, lake and pond water. 
         [0056]    When the coalescent efficient glycol ethers are mixed with the other carbinol materials, the ratio of the other carbinol materials to the coalescent efficient glycol ethers is in the range of from 0.1:99.9 to 25:75. The salts can be managed in the same manner. 
         [0057]    The compositions of the invention are easily prepared by simple mixing of the ingredients at room temperature and, the compositions can be stored indefinitely at room temperature. 
         [0058]    The following examples illustrate the disclosure. 
       Examples 
       [0059]    In accordance with UL 2901:  Outline of Investigation for Antifreeze Solutions for Use in Fire Sprinkler Systems  initial testing on potential solutions includes Pour Point—ASTM D97, Standard Test Method for Pour Point of Petroleum Products Viscosity—ASTM D2983, Standard Test Method for Low-Temperature Viscosity of Lubricants Measured by Brookfield Viscometer; Specific Gravity—ASTM D1429, Standard Test Methods for Specific Gravity of Water and Brine; pH—ASTM D1293, Standard Test Methods for pH of Water; Freeze Point—ASTM D6660, Standard Test Method for Freezing Point of Aqueous Ethylene Glycol Base Engine Coolants by Automatic Phase Transition Method or equivalent differential scanning calorimetric methods. All of these methods were used in acquiring the data in the following examples. 
         [0060]    After these required tests are met and quantified, the following further testing is required: High Ambient Temperature Stability; Temperature Cycling Stability; Electrical Conductivity; Corrosion Rate; Exposure to Elastomeric Materials; Compatibility with Polymeric Materials, and Exposure to Fire. 
         [0061]    In these examples, all data is in grams; Temperatures are measured in Centigrade (degrees C); Freeze Point at −20° C. was determined by placing samples in a refrigerated chamber for 24 hours at a constant −20° C. After 24 hours the sample was evaluated for flow; pH was tested using the  Standard Methods for examination of water and wastewater standard  4500-H. 
         [0062]    Exotherm or endotherm was measured using a NIST certified thermometers; Viscosity was tested using ASTM D2983, Standard Test Method for Low-Temperature Viscosity of Lubricants Measured by Brookfield Viscometer Model DV-II; Spindle 2 @100 rpm or Ubbleode tubes for low viscosity measurements. 
         [0063]    Freeze Point at −40° C. (or lower) was determined by placing samples in a bath of Dow Corning® 10 cst 200 fluid chilled to temperature using either a bath of dry ice in acetone or a Neslab Bath Cooler Model PBC 2-II; Pour point was determined by placing samples in a bath of Dow Corning® 10 cst 200 fluid™ chilled to temperature using either a bath of dry ice in acetone or a Neslab Bath Cooler Model PBC 2-II and observing the temperature at which the sample was no longer fluid. 
         [0064]    Corrosion rate was determined by placing pre-weighed samples into the test solution, aged at 49° C., and re-weighed at the prescribed times; Exposure to Elastomeric Materials was determined by placing pre-weighed samples into the test solution, aged at 70° C., and reweighed at the prescribed times, and, Unless specified otherwise all raw materials were purchased form Aldrich Chemical Company. 
         [0065]    Tables 1 and 2 represent the development work done to arrive at the lowest freezing point achievable. This effort centered on dissociative salts trying to achieve a freezing point of at least −40° C. 
         [0066]    The compositions of this invention can have conductivity properties that can be manipulated at will as will be obvious from the data infra. For example, city water, in the inventor&#39;s laboratory, has a conductivity of 300 μS. A requirement for the materials used for antifreeze for outdoor file suppression systems is 1000 μS or less. Table 3 sets forth conductivity for the various components and combinations useful in this invention. H+H 2 O is ultra-pure water. “Water” indicates tap water. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                 sample No. 
               
             
          
           
               
                   
                 A 
                 B 
                 C 
                 D 
                 E 
                 F 
                 G 
               
               
                   
                   
               
             
          
           
               
                 Water 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 KC 2 H 3 O 2   
                 269 
                   
                   
                 201 
                 135 
                 70 
                 269 
               
               
                 NaC 2 H 3 O 2   
                   
                 94.9 
               
               
                 Glycerol, 
                   
                   
                 100 
                 25 
                 50 
                 75 
                 100 
               
               
                 pure 
               
               
                 FPt, −20 C. 
                 OK 
                 SOLID 
                 OK 
                 OK 
                 OK 
                 OK 
                 OK 
               
               
                 initial pH 
                 8.5 
                 7 
                 4.5 
               
               
                 final pH 
                 7 
                 7 
                 7 
                 7 
                 7 
                 7 
                 7 
               
               
                 Exotherm, @ 
               
               
                 mix 
               
               
                 Init temp 
                 23 
                 23 
                 23 
               
               
                 final temp 
                 9 
                 20 
                 23 
               
               
                 pour point 
                   
                   
                   
                   
                 , −52 C. 
                   
                 , −52 C. 
               
               
                 FPt, −40 C. 
                 solid 
                   
                 solid 
                   
                 OK 
                   
                 OK 
               
               
                 , −48 C. 
                   
                   
                   
                   
                 OK 
                   
                 OK 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
             
             
               
                   
                   
               
               
                   
                 Sample No. 
               
             
          
           
               
                   
                 H 
                 K 
                 L 
                 M 
                 O 
                 P 
               
               
                   
                   
               
             
          
           
               
                 Water 
                 100 
                 100 
                 100 
                 100 
                 100 
                   
               
               
                 KC 2 H 3 O 2   
                 269 
                 33.7 
               
               
                 Glycerol, 
                   
                   
                 100 
                 50 
                 10 
                 100 
               
               
                 raw 
               
               
                 S.G. 
                 1.55 
                 1.2 
                   
                   
                   
                 1.25 
               
               
                 FPt, −20 C. 
                 OK 
                 Slice 
                 2 
                 solid 
                 solid 
                 v 
               
               
                   
                   
                   
                 phase 
                   
                   
                 thick 
               
               
                 initial pH 
                 9 
                 7.5 
                 4.5 
                   
                 5 
               
               
                 final pH 
                 8 
                 7 
                 5 
                   
                 5 
                 4.53 
               
               
                 Exotherm, @ 
               
               
                 mix 
               
               
                 Init temp 
                 22 
                 22 
                 22 
                   
                 22 
               
               
                 final temp 
                 11 
                 21 
                 22 
                   
                 22 
               
               
                 Viscosity, 
                 32 
                 5 
                 20 
                   
                 3 
               
               
                 cps 
               
               
                 Sp 2 @ 100 rpm 
               
               
                 Freezing 
                 , −40 C. 
               
               
                 point 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 Sample 
                 9 
                 10 
                 11 
                 12 
                 13 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 H + H 2 O 
                 100 
                 50 
                   
                   
                 50 
               
               
                 Glycerin 
                   
                 50 
               
               
                 DPM 
                   
                   
                   
                 100 
                 50 
               
               
                 TPNB 
                   
                   
                 100 
               
               
                 Conductivity uS 
                 1.8 
                 3.6 
                 4.5 
                 0.08 
                 1 
               
               
                 FPt, −20 C. 
                 solid 
                 OK 
                 &lt;−75 
                 −83 
                 OK 
               
               
                 Flash Pt 
                   
                   
                 126 
                 75 
               
               
                 Density 
                   
                   
                 0.93 
                 0.95 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Sample 
                 I 
                 J 
                 K 
                 L 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Water 
                 100 
                 90 
                 45 
                 49 
               
               
                   
                 KC2H3O2 
                 135 
                 10 
                 5 
                 1 
               
               
                   
                 Glycerol 
                   
                   
                 50 
                 50 
               
               
                   
                 Wt. % KCHO 
                 57 
                 11 
                 5 
                 3.6 
               
               
                   
                 Conductivity, uS 
                 76000 
                 14400 
                 8500 
                 3600 
               
               
                   
                   
               
             
          
         
       
     
         [0067]    Table 4 contains data regarding the level of Potassium Formate as it relates to the conductivity vs concentration in solution. Tables 5 and 6 illustrate conductivity as it relates to three lower levels of Potassium Formate, no Potassium Formate, and the addition of specialty fluids to lower the freezing point of the formulation. The formulations in Table 7 contain date regarding the levels of water in the formulation and its effect on conductivity and pH. 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 5 
               
               
                   
                   
               
               
                   
                 Sample 
                 15 
                 16 
                 17 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 H + H 2 O 
                 50 
                 50 
                 50 
               
               
                   
                 DPM 
                 47.75 
                 47.75 
                 47.75 
               
               
                   
                 TPNB 
                 2.25 
                 2.25 
                 2.25 
               
               
                   
                 KCHO 
                 1 
                 0.6 
                 0.2 
               
               
                   
                 % H 2 O 
                 50 
                 50 
                 50 
               
               
                   
                 Conductivity uS 
                 3600 
                 1955 
                 785 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 6 
               
             
             
               
                   
                   
               
               
                   
                 Sample 
               
             
          
           
               
                   
                 15 
                 16 
                 17 
                 14 
                 18 
                 19 
               
               
                   
                   
               
             
          
           
               
                 H + H 2 O 
                 50 
                 50 
                 50 
                 50 
                 50 
                 50 
               
               
                 DPM 
                 47.75 
                 47.75 
                 47.75 
                 47.75 
                 40 
                 30 
               
               
                 TPNB 
                 2.25 
                 2.25 
                 2.25 
                 2.25 
                 10 
                 20 
               
               
                 KCHO 
                 1 
                 0.6 
                 0.2 
                 0 
               
               
                 Conductivity 
                 3600 
                 1955 
                 785 
                 2.5 
                 5.4 
                 2 
               
               
                 uS 
                   
                   
                   
                   
                   
                 phase 
               
               
                 FPt, −20 C. 
                 OK 
                 OK 
                 OK 
                 OK 
                 OK 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 7 
               
             
             
               
                   
                   
               
               
                   
                 Sample 
               
             
          
           
               
                   
                 20 
                 21 
                 22 
                 14 
                 23 
                 24 
                 25 
               
               
                   
                   
               
             
          
           
               
                 H + H 2 O 
                 450 
                 150 
                 100 
                 50 
                 25 
                 10 
                 5 
               
               
                 DPM 
                 47.75 
                 47.75 
                 47.75 
                 47.75 
                 47.75 
                 47.75 
                 47.75 
               
               
                 TPNB 
                 2.25 
                 2.25 
                 2.25 
                 2.25 
                 2.25 
                 2.25 
                 2.25 
               
               
                 % H 2 O 
                 90 
                 75 
                 66 
                 50 
                 36 
                 16 
                 9 
               
               
                 Conductivity 
                 13.9 
                 8.01 
                 5.07 
                 2.5 
                 6.2 
                 5.81 
                 5.51 
               
               
                 uS 
               
               
                 pH 
                 7.57 
                 7.3 
                 7.02 
                 6.6 
                 6.2 
                 5.8 
                 5.5 
               
               
                   
               
             
          
         
       
     
         [0068]    Tables 8 and 9 are miscellaneous salt additives as they relate to freezing point while Table 10 shows the optimum formulations that have resulted in low conductivity and low freezing point depression. Additionally an added corrosion inhibitor to further improve the formulation was incorporated, i. e. CH 3 COOK and/or CH 3 COONa. 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 8 
               
               
                   
                   
               
               
                   
                 Sample 
                 20 
                 21 
                 22 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Water 
                 100 
                 100 
                 100 
               
               
                   
                 CH 3 COOK 
                 200 
               
               
                   
                 CH 3 COONa 
                   
                 125 
               
               
                   
                 NaCl 
                   
                   
                 35 
               
               
                   
                   
                   
                 ppt 
               
               
                   
                 FPt, −20 C. 
                 OK 
                 solid 
                 some ice 
               
               
                   
                 initial pH 
                 9 
                 9 
                 6.8 
               
               
                   
                 final pH 
                 9 
                 8 
                 6.8 
               
               
                   
                 Exotherm, @ mix 
               
               
                   
                 Init temp 
                 21 
                 21 
                 21 
               
               
                   
                 final temp 
                 26 
                 32 
                 19 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 9 
               
             
             
               
                   
                   
               
               
                   
                 Sample 
               
             
          
           
               
                   
                 a-13 
                 a-14 
                 a-20 
                 a-21 
                 a-3 
                 a-4 
                 a-7 
               
               
                   
                   
               
             
          
           
               
                 Water 
                 100 
                   
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 KC 2 H 3 O 2   
                   
                   
                 269 
                 135 
                   
                 269 
                 33.7 
               
               
                 prop glycol 
                   
                   
                   
                   
                 100 
                 100 
                 50 
               
               
                 Na Lactate 
                 100 
                 100 
               
               
                 Na Silicate 
                   
                   
                 26.9 
                 13.5 
               
               
                 FPt, −20 C. 
                 Solid 
                 Solid 
                 OK 
                 OK 
                 OK 
                 OK 
                 OK 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 10 
               
               
                   
               
               
                 Sample 
                 29 
                 30 
                 17 
                 15 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 H + H 2 O 
                 50 
                 50 
                 50 
                 50 
               
               
                 DPM 
                 47.75 
                 47.75 
                 47.75 
                 47.75 
               
               
                 TPNB 
                 2.25 
                 2.25 
                 2.25 
                 2.25 
               
               
                 DCC 6083 
                 1 
                 0.5 
               
               
                 KCHO 
                   
                 0.1 
                 0.2 
                 1 
               
               
                 % H 2 O 
                 50 
                 50 
                 50 
                 50 
               
               
                 Conductivity uS 
                 967 
                 857 
                 785 
                 3600 
               
               
                 FPt, −20 C. 
                 OK 
                 OK 
                 OK 
                 OK 
               
               
                 FPt, −C. 
                   
                 −20 
               
               
                 R.I. 
                 1.3907 
                 1.4255 
               
               
                 pH 
                 11.5 
                 10.7 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 11 
               
             
             
               
                   
               
               
                 Aging Study 
               
             
          
           
               
                   
                 Formulations 
                 130 
                 131 
                 132 
               
               
                   
                   
               
             
          
           
               
                   
                 same as 
                 30 
                 24 
                 32 
               
               
                   
                 H + H 2 O 
                 50 
                 10 
                 10 
               
               
                   
                 DPM 
                 47.5 
                 47.75 
                 47.75 
               
               
                   
                 TPNB 
                 2.25 
                 2.25 
                 2.25 
               
               
                   
                 DCC 6083 
                 0.5 
                   
                 0.5 
               
               
                   
                 KCHO 
                 0.1 
                   
                 0.1 
               
               
                   
                 % H 2 O 
                 50 
                 16.7 
                 16.5 
               
               
                   
                   
               
             
          
         
       
     
         [0069]    High Ambient Temperature Stability at 70° C. for 90 days . The Pour Point, Viscosity, Specific Gravity, pH and Freeze Point will remain stable within 10 percent of the initial properties (FIG. 2). Temperature Cycling Stability at 66° C. for 40 cycles. One cycle was equal to 24 hours at 66° C. and 24 hours at room temperature. The Pour Point, Viscosity, Specific Gravity, pH and Freeze Point will remain stable within 10 percent of the initial properties (FIG. 2). Corrosion Rate. The corrosion rate should not exceed 1.0 mils/year. Corrosion rate was tested according to NFPA 18A-2011. Metal alloy samples were submerged in the test solutions and incubated at 45° C. for 30, 60 and 90 days. The corrosion rate (Cr) was calculated using the following equation: 
         [0000]    
       
         
           
             
               Cr 
               = 
               
                 weight 
                  
                 
                     
                 
                  
                 loss 
                  
                 
                     
                 
                  
                 
                   ( 
                   g 
                   ) 
                 
                 × 
                 K 
               
             
             
               alloy 
                
               
                   
               
                
               density 
               × 
               exposed 
                
               
                   
               
                
               area 
               × 
               exposure 
                
               
                   
               
                
               time 
             
           
         
       
     
         [0000]    where K=5.34*10 5  
 
Percent Weight Loss was also calculated for these samples where:
 
         [0000]    
       
         
           
             
               % 
                
               
                   
               
                
               Weight 
                
               
                   
               
                
               Loss 
             
             = 
             
               
                 
                   initial 
                    
                   
                       
                   
                    
                   weight 
                 
                 - 
                 
                   final 
                    
                   
                       
                   
                    
                   weight 
                   × 
                   100 
                 
               
               
                 initial 
                  
                 
                     
                 
                  
                 weight 
               
             
           
         
       
     
       See FIG.  3 . 
       [0070]    Exposure to Elastomeric Materials: A volume change of minus 1 to plus 25 percent and a maximum loss of weight of 10 percent (See the Figures). 
         [0071]    Tables  12 ,  13 , and, illustrate a few of the compositions of this disclosure. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 12 
               
             
             
               
                   
                   
               
               
                   
                 sample No. 
               
             
          
           
               
                   
                 A 
                 B 
                 C 
                 D 
                 E 
                 F 
                 G 
               
               
                   
                   
               
             
          
           
               
                 Water 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
                 100 
               
               
                 KC 2 H 3 O 2   
                 269 
                   
                   
                 201 
                 135 
                 70 
                 269 
               
               
                 NaC 2 H 3 O 2   
                   
                 94.9 
               
               
                 Glycerol, pure 
                   
                   
                 100 
                 25 
                 50 
                 75 
                 100 
               
               
                 Freeze Pt, 
                 OK 
                 SOLID 
                 OK 
                 OK 
                 OK 
                 OK 
                 OK 
               
               
                 −20 C. 
               
               
                 initial pH 
                 8.5 
                 7 
                 4.5 
               
               
                 final pH 
                 7 
                 7 
                 7 
                 7 
                 7 
                 7 
                 7 
               
               
                 Exotherm, 
               
               
                 @ mix 
               
               
                 Init temp 
                 23 
                 23 
                 23 
               
               
                 final temp 
                 9 
                 20 
                 23 
               
               
                 Ratio 
                 100/0 
                   
                 0/100 
                 75/25 
                 50/50 
                 25/75 
                 100/100 
               
               
                 Viscosity 
               
               
                 S.G. 
               
               
                 pour point 
                   
                   
                   
                   
                 −52 C. 
                   
                 −52 C. 
               
               
                 R.I. 
               
               
                 Freeze Pt, 
                 solid 
                   
                 solid 
                   
                 OK 
                   
                 OK 
               
               
                 −40 C. 
               
               
                 −48 C. 
                   
                   
                   
                   
                 OK 
                   
                 OK 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 13 
               
             
             
               
                   
                   
               
               
                   
                 Sample No. 
               
             
          
           
               
                   
                 H 
                 K 
                 L 
                 M 
                 O 
                 p 
               
               
                   
                   
               
             
          
           
               
                 Water 
                 100 
                 100 
                 100 
                 100 
                 100 
                   
               
               
                 KC 2 H 3 O 2   
                 269 
                 33.7 
               
               
                 Glycerol, raw 
                   
                   
                 100 
                 50 
                 10 
                 100 
               
               
                 S.G. 
                 15.5 
                 1.2 
                   
                   
                   
                 1.25 
               
               
                 Freeze Pt, −20 C. 
                 OK 
                 Slice 
                 2 
                 solid 
                 solid 
                 v 
               
               
                   
                   
                   
                 phase 
                   
                   
                 thick 
               
               
                 initial pH 
                 9 
                 7.5 
                 4.5 
                   
                 5 
               
               
                 final pH 
                 8 
                 7 
                 5 
                   
                 5 
                 4.53 
               
               
                 Exotherm, @ mix 
               
               
                 Init temp 
                 22 
                 22 
                 22 
                   
                 22 
               
               
                 final temp 
                 11 
                 21 
                 22 
                   
                 22 
               
               
                 Viscosity 
                 32 
                 5 
                 20 
                   
                 3 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 14 
               
               
                   
                   
               
               
                   
                 a = 8 
                 a-9 
                 a-10 
                 a-13 
                 a-14 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Water 
                 100 
                 100 
                 100 
                 100 
                   
               
               
                   
                 KC 2  H 3  O 2   
                 269 
                 135 
                 135 
               
               
                   
                 prop glycol 
               
               
                   
                 eth glycol 
               
               
                   
                 Glycerol 
                   
                   
                 50 
               
               
                   
                 Corr. In @ 43% 
                 26.9 
                 13.5 
                 13.5 
               
               
                   
                 Na Lactate 
                   
                   
                   
                 100 
                 100 
               
               
                   
                 S.G. 
               
               
                   
                 FPt, −20 C. 
                 OK 
                 OK 
                 OK 
                 Solid 
                 Solid 
               
               
                   
                 initial Ph 
               
               
                   
                   
               
               
                   
                 Corrosion inhibitor = sodium trihydroxysilylpropyl methylphosphonate