Abstract:
The specification discloses a self-hardening mold sand having surface stability and high compressive strength yet containing a comparatively small amount of water. The mold sand is prepared by mixing a self-hardening binder of clinker powder, containing 11CaO.7Al 2  O 3 . CaX 2  (where X is a halogen atom) and a sulphate, with a binder additive consisting of a surface active agent of which the main component is β-naphthalene-sulphonic acid formaldehyde condensate salt, and then mixing this binder and binder additive with sand, water and preferably a retarder consisting of an organic carboxylic acid or boric acid.

Description:
This is a continuation of application Ser. No. 535,169, filed Dec. 23, 1974, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to self-hardening mold sand with a comparatively small moisture content, yet having high surface stability and compressive strength. 
     Prior artisans have provided self-hardening binders for mold sand which harden fast even at low temperature. These binders are made by adding insoluble anhydrite to clinker powder containing calcium haloaluminate of 11CaO.7Al 2  O 3 .CaX 2  (X refers to halogen atom). 
     Now mold sands for casting are being manufactured by mixing binder, or binder with additives such as various kinds of sulphate (for ex. sodium sulphate, calcium sulphate, hemihydrate) and/or with carboxylic acid or boric acid, with fire-resistant granules such as silica sand or olivine sand to develop strength of the sand in a short time. 
     To facilitate pounding of such mold sands thoroughly, a proper volume of water should be added to achieve proper compressive strength. If too much water remains, casting will not be effected well due to occurrence of &#34;blow&#34; at the time of casting material. Also the stability of mold surface will become low after cured due to &#34;brittle binding&#34; of sand. This causes &#34;scab&#34; and &#34;sand burning.&#34; 
     Water also enhances surface stability. The improvement of surface stability of mold has been attempted for example by increasing binder to enhance the strength of sand or by adding starch to the sand. Yet such was not satisfactory with respect to permeability of the mold, mositure content and fire-resistance of the mold sand. 
     SUMMARY OF THE INVENTION 
     The object of the present invention is to produce mold sand having good surface stability and proper compressive strength of the mold while using only a comparatively small amount of water. 
     The self-hardening mold sand of the present invention is prepared by mixing sand with binder additive and water. The binder additive is composed of self-hardening binder and a surface active agent. The surface active agent has as its main component, β-naphthalene sulfonic acid-formaldehyde condensate salt, of which the average condensation degree (n) is greater than 5, and of which the salt is a mixture of any one or more kinds of sodium, potassium and calcium. The self-hardening binder is composed of clinker powder, containing calcium haloaluminate of 11Ca0.7Al 2  O 3 .CaX 2  (where X is halogen), and sulphate. 
     The amount of the calcium halo-aluminate contained in the clinker powder is more than 2%, preferably more than 5% in view of initial fast hardening, still more preferably more than 10% to help insure that mold properties of air permeability, fire resistance and recovery are not injured. 
     The sulphate used as an additive to the clinker powder is an anhydrite, or has an anhydrite as its main part. Any combination of hemihydrate or dihydrate of calcium sulphate, sodium sulphate, potassium alum and sodium alum may be added thereto. The amount of sulphate is to be from 0.5 to 2.0 as the molar ratio Al 2  O 3  /SO 3  in the self-hardening binder. 
     The amount of binder additive to be added to the sand is from 2 to 20% depending on the amount of calcium halo-aluminate in the clinker powder, and preferably the amount is from 3 to 12% to obtain initial fast hardening and physical properties of mold sand. 
     The amount of the surface active agent to be added to sand is from 0.02 to 1.0% preferably from 0.05 to 0.5% depending on its effect and economical viewpoint. 
     Preferably, an organic carboxylic acid or boric acid is added to the mix as a retarder. The organic carboxylic acid to be used are succinic acid, adipic acid, tartaric acid, citric acid, gluconic acid, acetic acid and their sodium, potassium and calcium salts. The boric acid to be used includes such water soluble borates as boric acid, borax and boric anhydride. 
     The characteristics of the mold sand of the present invention are as follows: 
     (a) The surface of mold sand after curing exhibits a good surface stability. 
     (b) Hence the added water can be reduced without changing operation, and the moisture content of the mold sand after curing becomes very low. 
     (c) The strength of mold is high so that less troubles occur as compared with conventional molds. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 shows a diagrammatic curvature representing the relation of compressive strength to time elapsed for mold sands made pursuant to test samples (1)-(9) in Experiment I. 
     FIG. 2 shows a diagrammatic curvature representing the relation of the compressive strength of mold sands to the volume of added water pursuant to test samples (1)-(7) in Experiment II. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     Now the particulars of the present invention are explained with reference to the experiments as below. 
     Experiment I 
     In Experiment I, the following materials were used to produce mold sands of different formulations: 
     (a) Sand: Silica sand from MIZUNAMI No. 5 with particle size distribution mainly from 28 mesh to 48 mesh 
     (b) Binder: Two alternative special super high early strength cements were used whose compositions and fineness are shown in Table I, labeled b1 or b2. 
     (c) Surface active agent (four alternatives): 
     C1; a sodium salt of condensation products of β-naphthalene-sulphonic acid and formaldehyde of which condensation degree (n) is equal to 8, the surface active agent used in the present invention 
     C2; Polycyclic sodium sulphonate (of which components are for example) ##STR1## C3; alkyl aryl sulphate (a calcium salt of condensation products of naphthalenesulphonic acid and formaldehyde n=2.5) 
     C4; lignin derivative 
     (d) Bench life control agent (Retarder): 
     d1; citric acid 
     d2; boric acid 
     
                       TABLE I______________________________________BinderComposition         Kind of Binderand Fineness        Binder b1                        Binder b2______________________________________C.sub.11 A.sub.7 Ca F.sub.2 *(See below for               21%      21%explanation ofsymbols used)C.sub.3 S*          51%      51%C.sub.2 S*          3%       3%Ca SO.sub.4         16%      14%C.sub.4 AF*         7%       7%Ca SO.sub.4 1/2 H.sub.2 O               0%       2%Miscellaneous**     2%       2%Specific Surface Area               5,400    5,600by Blaine Air Permeability               cm.sup.2 /g                        cm.sup.2 /g______________________________________ *Explanation of symbols used in Table I C.sub.11 A.sub.7 CaF.sub.2 = 11CaO . 7Al.sub.2 O.sub.3 . CaF.sub.2 C.sub.2 S = 2CaO . SiO.sub.2 C.sub.3 S = 3CaO . SiO.sub.2 C.sub.4 AF = 4CaO . Al.sub.2 O.sub.3 . Fe.sub.2 O.sub.3 **Misc. = Salts such as Na.sub.2 SO.sub.4, K.sub.2 SO.sub.4, MgO, TiO.sub.2 
    
     Table II shows the mix proportions of the various materials described above used to create different formulations of mold sand. In mold sands, (1) (2) (3) and (4), the surface active agent of the present invention (Cl) is used. In mold sands (5) (6) and (7), surface active agents other than that of the present invention are used. References (8) and (9) show two mold formulations without any surface active agent. 
     
                       TABLE II______________________________________Mold Sand Mix ProportionsUnit: Parts by WeightPro-  Test Samplepor-  Present Invention                 Referencetion  (1)    (2)    (3)  (4)  (5)  (6)  (7)  (8)  (9)______________________________________Silica 100    100    100  100  100  100  100  100  100SandBinder 8      8      0    8    8    8    8    8    0b1b2    0      0      8    0    0    0    0    0    8Sur-faceActiveAgent 0.10   0.05   0.05 0.20 --   --   --   --   --C1C2    --     --     --   --   0.25 --   --   --   --C3    --     --     --   --   --   0.2  --   --   --C4    --     --     --   --   --   --   0.2  --   --Water 6      6      6    6    6    6    6    6    6Re-tard-er    .008   .008   .004 --   .012 .012 .012 .012 .008d1Re-tard-er    --     --     --   0.04 --   --   --   --   --d2______________________________________ 
    
     Table III shows the character of the mold sands (1)-(9) prepared pursuant to Table II. 
     
                                           TABLE III__________________________________________________________________________Character of the Table II Mold Sands  Test Sample  Present  Invention       ReferenceCharacter  (1) (2) (3) (4) (5)                     (6)                        (7)                           (8) (9)__________________________________________________________________________Bench life(minute)  40  40  40  40  40 40 40 40  40CompressiveStrength after24 Hours(kg/cm.sup.2)  27.0      25.8          26.4              28.6                  17.7                     17.0                        8.0                           20.7                               21.8Percentage ofCompressiveStrength (%)  130 125 121 138 85.5                     82.3                        38.6                           100 100SurfaceStability (%)  98.0      94.8          95.5              97.3                  88.0                     86.4                        68.3                           88.9                               89.6__________________________________________________________________________ 
    
     FIG. 1 shows the change of compressive strength relative to time elapsed for each of the mold sand formulations 1-9. 
     In the strength test of Table III, compressive strength is measured according to JIS Z-2604 (Japan Industrial Standard Z-2604). Surface stability is measured with a 6-mesh sieve mounted on a Sieve Analysis Machine provided with a vibrator. After 24 hours, each test sample is placed on the sieve and vibration is given to the sieve and sample for one minute. Then the weight of sample is measured. Surface Stability=W/WO×100 (%) where 
     WO; Initial weight of sample 
     W; Weight of sample after vibration 
     As apparent from FIG. 1 and Table III, while the surface stability of the reference mold sands (5)-(9) is below 90%, those (1)-(4) of the present invention show surface stability as high as 95-98%. That is, in the present invention, the surface stability is normally aimed to be higher than 90%. While it may be possible to formulate prior art compositions having 90% or higher surface stability, these prior art formulations would have defects in permeability and fire-resistance and cannot produce good cast surface. In particular, 93% or higher stability is aimed for practical use. Considering this, it has been proved that very high surface stability mold sand can be obtained with the present invention. Where other surface active agents are used, the surface stability is approximately the same or lower than that achieved without surface active agent. 
     As to the compressive strength, the surface active agent of the present invention shows that far better results can be obtained than with other surface active agents or than without surface active agents. 
     Experiment II 
     The same sand and binders of Experiment I are used. The relation between compression strength of mold sand and added water is determined using samples of (1)-(7) in Table IV. The results are shown in FIG. 2. Character of these mold sand samples is shown in Table V. Moisture content is measured after 24 hours according to JIS Z-2605. 
     
                       TABLE IV______________________________________Mold Sand Mix ProportionsUnit: Weight   Sample   Reference   Present InventionComposition     (1)    (2)    (3)   (4)  (5)  (6)  (7)______________________________________Silica Sand     100    100    100   100  100  100  100Binder b1 10     10     10    10   10   10   10SurfaceActiveAgent C1  0      0      0     0.125                              0.125                                   0.125                                        0.125Water     6      5      4     6    5    4    3CitricAcid      0.015  0.015  0.015 0.01 0.01 0.01 0.01______________________________________ 
    
     
                       TABLE V______________________________________Character of the Table IV Mold Sands    Sample    Reference  Present InventionCharacter  (1)    (2)    (3)  (4)  (5)  (6)   (7)______________________________________Bench Life(minute)   40     40     40   40   40   40    40CompressiveStrength after24 Hours(kg/cm.sup.2)      28.0   23.6   12.0 31.7 29.5 22.3  7.6SurfaceStability (%)      92.3   90.0   72.2 98.3 97.5 89.8  63.1Moisture Content(%)        2.34   2.06   1.31 2.31 1.92 1.47  1.12______________________________________ 
    
     As is apparent from Table 5 and FIG. 2, in the present invention, for example in sample (6), where 4%, water is added, the compressive strength is 22.3 kg/cm 2  and the surface stability 89.8%, while in sample (2) in the reference, where 5% water is added, approximately same compressive strength 23.6 kg/cm 2  and surface stability 90.0% are shown. Therefore in the present invention some 20% less water can be added and the desirable results of adding more water can be achieved without suffering the drawbacks of adding more water. 
     Also comparison is made as to additive between sample (5) and sample (1). In respect of compressive strength, the two are almost at the same level. However with respect to surface stability, 97.5% in sample (5) is far better than 92.3% in sample (1). Also in the present invention, water addition can be reduced 20% below the conventional. 
     Therefore in the present invention, moisture content may become less than 2%, while without the additive of this invention, it is very hard to reduce moisture content to less than 2%. 
     FINAL EXAMPLE 
     To &#34;Enshu&#34; silica sand (No. 6 of which particle size distribute mainly from 48 mesh to 100 mesh) in ratio (weight) shown in Table VI below, Jet Cement (commercial name of the product of Onoda Cement Co., Ltd.) mineral composition of 11CaO.7Al 2  O 3 .CaF 2  20.6%, β-naphthalenesulphonic condensate sodium salt (average condensation degree 8), sodium salt of gluconic acid soda, were mixed with water. Bench, life, compressive strength, and surface stability of the cured product (sample of after 24  hours after mixing) were measured and the results are shown in the lower part of Table VI. 
     
                       TABLE VI______________________________________                No.Mixture &amp; Physical Property                  1        2______________________________________Mixture &#34;Enshu&#34; silica sand                      100   100   Jet Cement         8     8   β-naphthalene-sulphonic acid   formaldehyde condensate   sodium salt        0.2   0.2   Sodium salt of gluconic acid                      0     0.01   Water              6     6Physical   Bench life (minutes)                      20    40Property   Compressive strength   (kg/cm.sup.2) 2 hours                      4.9   2.4   Compressive strength   (kg/cm.sup.2) 24 hours                      32.2  33.4   Surface Stability (%)                      99.2  98.5______________________________________