• 专利附录
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    • 专利摘要:
    Binder compsn suitable for use with refractory mouldings, abrasive articles, foundry casting moulds and cores, comprises 50-95 wt % boron contg. aluminium phosphate together with an alkaline earth substance, mixed with 5-50 wt % of aluminium phosphate with alkaline earth substance. The boron contg. aluminium phosphate contains 5-30(10-25) mole % B wrt Al and the molar ratio phosphorus to al/P is 2.5-3.5:1 (2.8-3.2:1). The compsn. has increased mechanical strength, shock resistances and resistance to bending compared with binders of similar compsn. but contg. no B.
    公开号:SU876052A3
    申请号:SU742078664
    申请日:1974-11-13
    公开日:1981-10-23
    发明作者:Х.Тоенискоеттер Ричард；Дж.Спивак Джон
    申请人:Эшланд Ойл,Инк. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to foundry, namely, the compositions of the masses, compositions or mixtures used to make foundry cores and molds, as well as refractory and abrasive products.
    Closest to the invention in its technical essence and sufficiently, the result is a pulp for making casting cores and molds, containing a refractory filler and a complex binder based on alumini phosphate, water and an alkaline earth metal oxide-based material, namely magnesium oxide El
    This mass is characterized by insufficient adhesion strength of the refractory filler particles, as a result of which the OT-I removal of the implanted products “from the rigging” creates the potential for cracks in the products (cores, molds, refractories and abrasive products) and a sharp deterioration of their operational properties. properties ..
    The aim of the invention is to increase the adhesion strength of the particles of the refractory filler and prevent the formation of cracks when removing items from the tooling.
    To achieve this goal, the mass for the manufacture of foundry: cores and molds, as well as refractory and abrasive products, including refractory filler and integrated aluminum-phosphate-based binding base, contains, in combination with water and oxide-based material, as a complex binder. Alkaline earth metal compounds with the following Co-Ratio and of ingredients in wt.%:
    Fireproof refill 60,0-99,5
    A complex binder 0, 5-40.0, with the ingredients for a 1-plex binder, namely, borated phosphate of aluminum, in combination with water and a material based on an alkaline earth metal oxide compound in the following ratio, in weight. %:.  Borned aluminum phosphate 25, Water 5,7-63. , 4 A material based on an oxide compound of an alkaline earth metal 2.6-46.0, while the boron content in boron cm phosphate of aluminum is 0.08-1.9 weight. % at the weight ratio of the phosphorus content to the total aluminum and boron content (1.98: 1) U4.54: l).  As a material based on an alkaline earth metal oxide compound, the proposed mass may contain an alkaline earth metal oxide or hydroxide.  An example of a material of this group is magnesium oxide.  As a material based on an alkaline earth metal oxide compound, the proposed mass may contain natural alkaline earth metal chemical compounds including, along with alkaline earth metal and its oxide, oxide compounds of elements selected from the group of the following series: silicon, aluminum, cirrnium, boron, titanium.  An example of the material of this group are silicates, aluminosilicates, aluminates, zirconate borates, alkaline earth metal titanates.  As a material based on an alkaline earth metal oxide compound, the proposed mass can contain an alkaline earth metal oxide or hydroxide in combination with a natural chemical compound of an alkaline earth metal, including oxide metal with its oxide and oxide compounds of elements selected from the group of the next series: silicon , aluminum, zirconium, boron, titanium, with a weight ratio (2: 1) - (8: 1) between an oxide or a hydroxide-alkaline earth metal and the specified natural chemical compound earth metal.  The listed types of materials based on an alkaline earth metal oxide compound are characterized by a specific surface area of 0.01–8.5 m / g measured by the method of low-temperature nitrogen adsorption (by the BET method).  The binder material itself is boron phosphate aluminum (BPA).  It contains 3-40, preferably 5-30, preferably 10 25 gram-atomic percent of boron per gram-atomic amount of aluminum, and the ratio of gram-atoms of phosphorus to the sum of gram-atoms of aluminum and boron is in it (2: 1 ) (4: 1). preferably (2.5:) - (3.5: 1, preferably (2.8: 1) - (3.2: 1).  To obtain BPA, phosphorus, boron, and alum containing components are used.  As phosphorus-containing component, orthophosphoric acid with a concentration of 70-86 wt. %, preferably 86%.  It is possible to use phosphoric anhydride, polyphosphoric. acids, etc. P.  AT. The use of boric acid is preferable as a boron-containing component, although other boron-containing substances are not excluded, for example, boric anhydride, alkali metal borates, etc. P.  As the alumina-containing component, it is preferable to use the alkimini oxide trihydrate Ae203-ZN20.  The reaction between the components indicated as preferred proceeds with an exothermic effect, therefore, for the initial heating, mechanical mixing of these components is sufficient.  At the same time, the temperature of the reaction mixture spontaneously rises to EZ-IO C.  Upon reaching this temperature in order to complete the reaction, the reaction mixture is heated for 0.52 h to 105-121 C.  The total duration of the reaction for the complete formation of VFA is 1-4 hours, preferably 2-3 hours.  The other ingredient of the binder is water.  It may be fully or partially introduced into the binder system as a carrier for BPA.  But it can also be introduced into the molding compound as a separate component. Preferred, however, is when water is fully introduced into the finished BPA.  The water content is 1550 wt. %, mainly 2040 weight,%, calculated on the total weight of BPA and water.  The viscosity of the thus obtained aqueous solution of BPA is 100-2000 cP, preferably 200-1000 cP.  The use of BPA instead of aluminum phosphate, which does not contain boron atoms, allows to increase the final strength of the products from the molding material.  Boron contributes to a slight slowdown in the reaction between the interaction of aluminum phosphate and the oxide compound of the metal of the earth, thereby improving the ability to control the rate of cure | molding mass in the desired direction.  In addition, boron in the composition of BPA contributes to the stabilization of the strength of molded products, preventing their weakening during prolonged exposure to air.  Finally, boron in the composition of BPA contributes to a significant increase in the stability of aqueous solutions of BPA during storage, preventing the formation of sediment in them.  When boron content in BPA is lower than the stipulated lower limit from. Labeled effects are not observed or occur to a very low degree, and when it is contained in the VFA above the stipulated upper limit, the rate of interaction of the VFA with the oxide compounds of alkaline earth metals is excessively slowed down and, accordingly, the rate of cold curing of the products in the equipment decreases sharply.  Oxide-based material: Alkaline earth metal (OSCHM) in the complex binder system can be considered as repairer.  Examples of materials based on OSCHM include magnesium oxide, calcium oxide, calcium silicate, calcium aluminate, calcium aluminosilicates, magnesium silicate, magnesium aluminate. Alkaline earth metal zirconates, borates and titanate are also found.  Most preferably, free oxides of alkaline earth metals or mixtures consisting of free oxides of alkaline earth metals and substances which contain an alkaline earth metal and oxide in combination with other constituents such as calcium aluminate are used.  Preferred alkaline earth metal oxide is magnesium oxide.  As magnesium oxide, applicable are for example technical grades of magnesia and calcined magnesium oxide.  When using an OSCHM type of calcium silicate, wollastonite should be preferred - a high-purity mineral that contains calcium oxide and silicon dioxide in an equimolar ratio.  Technical calcium aluminate, which is also one of the examples of OShM, in most cases contains from about 15 to 40 percent by weight of calcium oxide and from about 35 to 80 weight percent of aluminum oxide, and the total amount of calcium oxide and aluminum oxide is at least 70 weight percent. Calcium aluminates with a higher calcium nitrous content may also be used.  Mixtures of free alkaline earth metal oxide and a substance containing, along with free oxide or hydroxide and alkaline earth metal, other constituents contain preferably from 1 to 10 parts by weight, preferably from 2 to 8 parts by weight of free alkaline earth metal oxide, per 1 weight part of the substance, containing other components.  Preferably, combinations of this type consist of magnesium oxide and calcium aluminate.  The free alkaline earth metal oxide, for example, magnesium oxide, is primarily responsible in such mixtures for a fast curing rate, while other components, such as calcium aluminate, mainly improve the strength properties of the fabricated form.  .  To facilitate the handling of the compound, alkaline earth metals are used in some cases in the form of suspensions or suspensions in a liquid diluent.  As an example of a diluent, alcohols such as ethylene glycol and furyl alcohol, esters such as ethylene glycol alkyl ether acetates, hydrocarbons such as kerosene and naphtha and liquid aromatic hydrocarbons, as well as mixtures of these diluents, can be mentioned, in some cases in order to stabilize the suspension in it is added to 10 wt. %, preferably up to 5% by weight, of a suspending agent, in which, for example, montmorillonite derivatives, highly dispersed silicic acid or high molecular weight forming colloidal solutions, carboxyvinyl polymers, can be used.  The alkaline earth metal compounds and the diluent are mixed in most cases in a weight ratio of up to 3: 1, preferably from l2 to 2: 1.  In comparison with other diluents, non-polar hydrocarbons result in binders characterized by better strength properties.  Also, alcohols such as ethylene glycol and furyl alcohol are preferred diluents, since they increase vitality; molding masses without simultaneously increasing the curing time. However, in the case of the use of alcohols such as ethylene glycol and furyl alcohol, the strength properties of the casting molds deteriorate somewhat.  With the content of material based on OSShM in the composition of the complex binder below the stipulated lower limit, there is a slowdown in the speed of curing and molding material, and its content above the stipulated upper limit excessively reduces the durability of the molding material and makes it difficult to process.  The specific surface of the material based on OSShM, measured by the method of temperature-dependent adsorption a3ova (by the BET method), should be 0.18, 5, preferably 3. The less reactive with BPA is the material based on the SNRM, in particular, the lower the content of active free oxide or alkaline earth hydroxide. The metal should be selected (within the specified limits) specific surface area.  On the other hand, if the material based on OSShchM is predominantly or completely composed of active free oxide or alkaline earth metal hydroxide, its increased (close to the upper specified limit) specific surface area may lead to an undesirable reduction in mold durability.  In this case, it is necessary to use modern mixing preparation units that provide high intensity and minimal duration of mixing of the ingredients in the mass.  When the value of the specific surface of the materials based on OSShM below and above the specified limits, respectively, a slowdown in the curing rate and a decrease in the durability of the molding material are observed.  In both cases, the properties of the molding material do not meet the requirements of manufacturability.  As a refractory filler in the manufacture of casting molds and cores, it is preferable to use silica sand with a silica content of at least 70%, preferably not. less than 85% with an average grain size of 0.100-0.290 mm, for at least 80 wt. %, preferably 90 wt. % quartz sand In addition to quartz sand, it is possible to use other refractory fillers, for example, zircon, olivine, chromite, aluminosilicate sand4 To obtain molds for precise casting, a refractory filler is chosen that, at least 80%, mainly 90% of its mass, consists of grains with a size of 0.0440, 074 mm.  At the same time, fused quartz, zircon, magnesium silicate sand, such as olivine and aluminosilicate sand, can be used as a refractory filler.  In order to obtain refractory materials, for example, ceramic products, a porous filler is selected, which, at least by 80%, mainly 90% of its mass, consists of not more than 0/074 mm, preferably not more than 0.44 mm.  When used in the manufacture of fire resistant materials, the molding masses must withstand the curing temperature above, since refractory materials appropriate for their application are subjected to sintering.  Suitable refractory filler for such a purpose are, for example, high melting point oxide carbides, nitrides and silicides, for example alcumini, lead, chromium, zirconium and silicon oxide silicides, as well as carbide, titanium nitride, boron nitride molybdenum and a carbon containing substance like graphite.  You can also use combinations of these fillers or a combination of powders of metals and ceramic substances.  As an example of the substances that make up the particles for the manufacture of abrasive materials, alumina, silicon carbide, carbide, boron, corundum, garnet and shmigel can be mentioned, as well as combinations thereof.  The size of the abrasive grains is generally accepted for abrasive size.  Inorganic refractory fillers, such as cryolite, fluorspar, silicon dioxide, consisting of 85%, mainly 95%, can be added to the abrasive particles.  its mass of grains with a size of not 0.074 mm.  In this case, the content of said refractory filler is 1-30 wt. % of total abrasive and refractory filler.  It is preferable to use a refractory filler with a moisture content of about 0.3% for all applications of the foundry oil.  The content of the complex binder in the composition of the molding material is in the manufacture of casting cores and molds - no more than 10 weight. %, mostly 0.5-7 wt. %, preferably 1-5 weight. %; in the manufacture of cores and molds for precision casting and in the manufacture of refractory products - no more than 40 weight. %, mostly 5-20 wt. %; in the manufacture of abrasive products - no more than 25 wt. %, mostly 5-15 wt. %  With the content of the complex binder in the composition of the proposed molding material below the stipulated lower limit, the required strength of the products made from the mass is not achieved, and with the content of it above the stipulated upper limit, there is an unnecessary increase in the cost of products without achieving any new or technological advantages.  The proposed complex binder, as can be concluded from the above information, is stored and supplied as two separate parts that come in contact with each other only during the preparation of the mixture: the first part is WFA and water, the second part is matter based on ESSM .  The usual procedure for the preparation of the molding material involves mixing the material based on OC1CM with a refractory filler with the subsequent introduction and mixing of an aqueous solution of BPA.  In some s. When taking part, the molding compound may also contain known additives for service purposes.  for example, iron oxide, chopped flax fibers, wood flour, gly, and refractory materials.  The casting molding mass is screwed at room temperature during chemical recovery without being heated from the outside.  Curing takes place by the so-called air-cure or no-bake mechanism.  In this case, the curing temperature is usually in the range of about lO-SO C.  The casting molds obtained from the proposed mold mass have a good shrinkage resistance and high crack resistance at the time of removal from the tooling, and for this reason they are easy to use and can be used immediately after removal.  The field of application of rods and molds from the proposed mass is casting from chernilkh alloys (mainly iron) and casting from undesirable relatively low-melting non-ferrous alloys (ammonium alloys, copper, for example brass).  In contrast to the known molding compounds with a binder of sodium silicate (liquid glass), the proposed molding composition is characterized by a lightweight disintegration from castings.  In the case of pouring From color solutions, when the heating temperature of the walls and the forms is not sufficient for the required softening, it is proposed. In this way, the cleaning of castings is greatly facilitated by the fact that this softening occurs after the cores and molds are treated with water.  At the same time, the quality of the surface of the aluminum lithium is very high.  The invention is illustrated below.  Example w.  In all examples, the contents of the ingredients are given in parts by weight, and the curing of the molded samples for testing the NII takes place in air at room temperature.  (Except where otherwise indicated).  P p i. meper 1. With stirring, a reaction vessel equipped with a stirrer, a thermometer, and a reducing valve is charged with stirring 38,000 parts of an 80% aqueous solution of orthophosphoric acid, 307 parts of boric acid, and 7720 parts of hydrated alumina.  The reaction mixture is heated for 30 minutes before and then for the next 20 minutes, the reaction is carried out without external heating, and the temperature due to the heat of the exothermic reaction rises to a maximum value (about).  Immediately after this, the reaction mixture is additionally heated for 70 minutes to 113 C.  The pressure in the reaction cMecvi rises to 1.055 atms.  Then, the reaction mixture is cooled to 45 minutes within 45 minutes, and 5900 parts of water are simultaneously mixed with stirring.  Then the reaction mixture is cooled at a pressure of 76 mm Hg. Art.  The system is brought to atmospheric pressure and as a result, 52,000 parts of borated alkali phosphate with a solids content of 66.6% and viscosity from 250 to 300 cP are obtained, with a gram-atom ratio of phosphorus to the total grammatical amount of alnmini and boron 3 : 1 and a boron content of 5 gram atomic percent calculated on the grammatical amount of alk 1ini.  100 parts of foundry sand and 0.85 parts of a suspension of 0.4 parts of kerosene and 0.45 parts of magnesia with a specific surface area of 2.3.  stirred for 2 minutes. The sand contained 99.98% silica, 0.02% iron oxide, 0.10% alumina, 0.15% titanium dioxide, O, 01% calcium oxide and 0.005% magnesium oxide and had the following fractional composition: 0.4 % more than 420 microns, 11.2% more than 297 microns, 35.2% more than 210 microns, 37.4% more than 149 microns, 10.8% more than 105 microns, 4.0% more than 74 microns, 0.8% more 63 microns, 0.8% more than 53 microns, 0.2% more than 44 microns and 66.92% of the finely divided (dust) fraction (AFS).  3,, 2 parts of boron-containing aluminum phosphate were introduced into the mixture and stirred for another 2 minutes.  The resulting molding material for casting molds J and manually into standard samples to determine tensile strength (AFS standards).  The tensile strength of the test specimens at room temperature after 2 hours was. .  5.27 kgf / cm after 4 h -. 7.38 kGs / cm after 6 h - 9.84 kG / cm and after 24 h - 11.95 KGS / CM. The vitality (bench (ife)) of the molding material was 10 minutes, and the curing time (before removal from the tooling) was. from 35 to 40 min.  The resistance to cracking by the time of removal from the tooling was increased: and after 2 hours it became very high.  9 Example 2.  The method of preparing BFA described in Example 1 was repeated and used 3. , 5 weight. % of this BPA per molding sand.  The tensile strength of this molding material was at room temperature, after 2 hours, 5.27 kgf / cm — after 4 hours — 8.44 kgf / cm, after 6 hours — 10.2 kgf / cm, and after 24 hours - 11.6 kgf / cm.  Samples were highly resistant to cracking after 2 h.  The vitality of the mass was 10 min.  The time taken to extract the samples from the equipment was from 40 to 45 minutes.  Example 3  5000 parts of molding sand and 35 parts taken in a 2.5: 1 weight ratio of a mixture consisting of magnesium oxide and calcium aluminate with a content of 58% lkmknc oxide and 33% calcium oxide were mixed with each other for 2 minutes, then mixing with 165 parts of a 66% aqueous solution of BPA, which was prepared according to Example 1, after which the mixture was stirred for another 2 minutes.  The tensile strength at room temperature after 24 hours was 11.95 kgf / cm.  The durability of the molding material was 10 minutes; the curing time before removal from the tooling was 30 minutes.  By the time of extraction, the resistance to crack formation was.  good, and after 2 hours - great.  Example 4  The composition described in Example 3 was prepared using 30 parts of a mixture of magnesium oxide and calcium aluminate.  The tensile strength at room temperature after 2 hours was la 5.63 kgf / cm, after 4h11, 25 kgf / cm, after 6 h - 12.55 kgf / s, and after 24 h - 13.8 kgf / cm.  The survivability was 15 minutes, the time to remove the samples from the tooling was 45 minutes. / The following examples 5-9 show the influence of the specific surface area of magnesium oxide when used as OS-M material.  Example 5  5000 parts of quartz sand and 25 parts of magnesium oxide with a specific surface of 2.3 were mixed for 2 minutes.  Then, 165 parts of a 66% aqueous solution of BPA were added, which was prepared in accordance with Example 1, after which the mixture was stirred for 2 minutes.  The resulting mold mass had a vitality of 10 to 20 minutes.  Example 6  The composition described in Example 5 was prepared using magnesium oxide with a specific surface of 1.4 m vr, as well as 1 & FA with a boron content and an amount of 10 grams atomic% per gram atomic amount of aluminum.  The mold durability for the casting molds was 15 minutes.  Example 7  The composition described in Example 6 was prepared using magnesia with a specific surface of 35.2 MVr.  The survivability of the molding mass was less than 2 minutes, so mixing in this case should occur very quickly.  I Example 8.  The composition described in Section 6 was prepared using magnesia with a specific surface of 61.3 MVr.  The durability of the molding compound was less than 2 minutes.  which requires a very fast mixing method.  Example 9  The composition described in Example 5 was prepared using magnesia with a specific surface of 8.2 MVr, which was obtained by 24-hour calcination of a technical product with the trademark of Michigan 1782 at 1000 ° C.  Next, made mixing with BPA with a boron content of 30 gram-atomic% per gram-atomic content of aluminum.  The durability of the molding composition was from 2 to 4 minutes, so that the usual mixing method can be used.  But for some applications, this vitality may not be sufficient.  Example 10  Table 1 explains the effect of boron content in BPA on the vitality and curing time of the molding materials for casting molds.  Molding masses were obtained by mixing two thousand minutes of 5000 parts of quartz sand and the quantity indicated in Table 1 in a 2.5: 1 weight ratio of a mixture of magnesium oxide and calcium aluminate with a content of 58% alumina and 33% calcium oxide.  Then, 165 parts of the BFA solution specified in Table 1 were added to the mass, which was obtained with a gram-atomic content of phosphorus to the total gram-atomic amount of aluminum and boron 3: 1.  The tensile strength values obtained after 24 hours and after 48 hours curing at room temperature are given in Tables 2 and 3.  It can be seen that in most cases boron-containing aluminum phosphate leads to higher values of tensile strength than phosphate-aluminum without boron for stretching.  In addition, tensile strength in most cases increases with increasing content of boron in BPA.  Example 11  According to table 4, it can be concluded that the stability is improved during storage of aqueous solutions of aluminum phosphate when boron is added.  The following examples 12 and 13 are improved in comparison with known inorganic binders resistant.  resistance to cracking and shrinkage resistance when excavating a mold.   Example 12  20,000 parts of foundry sand and 200 parts of a mixture consisting of 60 parts of kerosene, 85.6 parts of magnesia and 34.4 parts of calcium aluminate containing 58% of alumina and 33% of calcium oxide were mixed for approximately 2 minutes.  Then, 660 parts of a 66% aqueous solution of BPA, prepared in accordance with example 1c with a viscosity of 250 to 300 cP, were added to the mixture, with a gram-atomic ratio of phosphorus to the total gram. The 1-atomic amount of aluminum and boron was 3: 1, and the boron content was 10 gram-atomic% per gram-atomic amount of aluminum.  Then the mixture was stirred additionally for 2 minutes.  After that, the obtained molding material was made by packing rods with a size of 1.1 bx 10.1 bx 45.72 and a weight of about 8.62 kg.  Vitality was 10 min. .  The extraction time of the rods from the tooling was 45 minutes.  The resistance of the rods to the formation of cracks, which is conventionally evaluated by hardness, amounted to an extraction point of 85-90 units, after 1 hour, 90-95 units.  After removing from the snap three rods. They were placed horizontally on the edge of the laboratory table so that the end of a length of 15–24 cm extended beyond the edge of the table.  After 1-hour exposure of the rods in the specified position, the deviation in relation to the horizontal position was determined which was no more than 1.59 mm. Another experiment to determine the deviation was carried out in such a way that three rods were either fixed onto the supports with their ends and were not fixed in the middle part, or fixed in the middle part, and the ends left free.  In addition, vertically tested. Rods that were installed on the ends with a surface of 10.16 x X 10.16 cm.  None of the rods showed a noticeable subsidence.  Also, when cured for 24 hours, sedimentation does not occur.  Two rods were manufactured with dimensions of 10.16 X 10.16 X 45.72 cm, in which hooks were inserted at a distance of 7.62 cm from each end to a depth of 5.08 cm.  After 30 minutes, one of the rods was lifted and hung at the ends in a horizontal position.  The rod settles and breaks after 3 minutes.  After 45 minutes, another rod is taken out and immediately placed in a horizontal position at the two ends.  For 24 hours he remained without noticeable settling in that position.  Example 13  5000 parts of foundry sand and 50 parts of a product consisting of 20 parts of heavy gasoline (flash point of 53.3 ° C, boiling point range from 180 to) and 30 parts of a mixture of magnesium oxide and calcium aluminate, which contained 58% alumina and 33% calcium oxide, with magnesium oxide and calcium aluminate in a 5: 1 weight ratio, stirred for 2 minutes.  The mixture was combined with 165 parts; a 7% aqueous solution of BPA with a ratio of gram atoms of phosphorus to the sum of gram atoms of aluminum and boron 3: 1 and with a boron content of 20 gram atoms per grammatical amount of aluminum and weight stirred for 2 minutes.  The tensile strength was about 5.27 after 2 hours, about 13.7 after 24 hours, about 13.2 after 48 hours, and about 13.0 kgf / cm after 120 hours.  The vitality of the molding grade was 17 minutes, and the extraction time of the samples from the tooling was 66 minutes.  The crack resistance at the time of removal from the tooling was very good.  PRI me R 14.  Example 13 was repeated, however, using 20 parts of heavy gasoline with a flash point of 40.6 and a boiling point range of 157 to 192 seconds.  The tensile strength at room temperature after 2 hours was about 4.92, after 24 hours about 13.2, after 48 hours about 13.9, and after 120 hours about 11.2 kgf / cmg. 16 minutes, and the time taken to take the samples from the equipment was 62 minutes.  Cracking resistance at the time of extraction was very good.  Example 15 - Example 13 was repeated, however, when using kerosene with a flash point of 48, and with a boiling point range between 171 and.  The tensile strength of the tested specimens was after 2 hours 6.54, after 4 hours - 11.9, after 6 hours-14.1, after 12 hours - 14.7 and after 96 hours 9, 5 kgf / cm.  The vitality of the molding mass was 16 minutes, and the time until samples were taken from the tooling was 60 minutes.  The crack resistance at the time of extraction was o4eHb good.   Example 16  In a reaction vessel equipped with a stirrer, thermometer and reflux condenser, 2445 parts of 85% phosphoric acid were loaded.  Then, with stirring, 67 parts of sodium borate were added and stirring continued until a clear solution was formed.  The resulting solution was mixed with 540 parts of hydrated alumina with stirring.  The reaction proceeded for about 40 minutes, and as a result of the reaction with the exothermic effect, the temperature rose to.   By additional heating, the temperature was raised to and maintained at the indicated level for 2 hours to complete the chilic interaction.  After cooling the reaction mixture to room temperature, 3052 parts of BPA with a solids content of 75%, a viscosity of about 40,000 centipoise, a ratio of gram atoms of phosphorus to a sum of gram atoms of aluminum and boron, 3: 1 and a boron content were obtained. e is about 10 grams-a volume% per gram-atomic amount of aluminum.  5,000 parts of foundry sand and 30. parts of a mixture of magnesium oxide and calcium aluminate with 58% alumina and 33% calcium oxide, with magnesium oxide and calcium aluminate in a 2.5: 1 weight ratio mixed for approximately 2 minutes.  To the mixture was added 165 parts of an aqueous solution of BFA (66% solids, viscosity from 400 to 500 cP) containing 146.5 parts prepared by the above method.  BPA and 18.5 parts of water were mixed for another 2 minutes.  The tensile strength of the tested samples was 8.8 at 2 hours after room temperature, 11.6 after 4 hours, 11.2 after 6 hours and 8.4 kg / cm after 24 4i.  The hardness of the test specimens was measured on a bore to determine the hardness of the 674 grade (Dieter), and by Lrich it was 2 hours 75 units. , through .  4 hours - 72 items in 6 hours - 74 units.  and after 24 hours - 65 units.  The survivability of the molding mass was 13 minutes, the exposure time before removal from the tooling was 42 minutes.  Example 17  16 is not repeated, however, when using phosphate aluminum that does not contain boron. aluminum phosphate contained 3 gram atoms of phosphorus per gram atom of aluminum. .  The tensile strength of the tested samples was 6.7 at room temperature after 2 hours, 10.5 each after 4 hours and 6 hours, and 6.7 kgf / cm after 24 hours. The survivability of the molding mass was 12 minutes, and the holding time until the samples were taken from the tooling was 35 minutes.  The hardness of the samples was after 2 hours 73, after 4 hours - 69,. after 6h70 and after 24 hours 7 66 units.  Comparison of examples 16 and 17 shows that the hardness and ultimate strength of foundry molds from the molding masses of the present invention are higher than when using non-boron-containing aluminum phosphate, which clearly indicates the values of tensile strength after 24 hours of storage.  Example 18  10,000 parts of foundry sand and 70 parts of a mixture consisting of magnesium oxide and calcium aluminum with 58% aluminum oxide and (33% calcium oxide, with magnesium oxide and calcium aluminate in a 2.5: 1 weight ratio, mixed for 2 minutes .  To the mixture were added 330 parts of the obtained BFA solution (66% solid content, viscosity from 250 to 300 cP) with a ratio of gram atoms of phosphorus to the sum of gram atoms of aluminum and boron 3: 1 with boron content in the amount of 20 gram atomic percent per gram atomic. the amount of aluminum, and then made stirring for another 2 minutes  Disk-shaped samples with a diameter of 17.8 cm and a thickness of 6.35 cm were made from the obtained molding composition for casting molds.  Disk-shaped samples (rods) on both sides in the direction of their axis had a rod sign with a diameter of 3.17 cm and a thickness of 1.27 cm.  The rod was placed in a sand form with a disc-shaped hollow space with a diameter of 20.3 cm and a height of Q, 9 cm, with a hole of 3.17 cm along the axis and a corresponding hole for pouring metal.  The rod was held in the desired position within the form with rod signs.  After pouring molten aluminum with a temperature of 816 ° C metal. ; allowed to cool to room temperature for 24 hours.  Immediately after this, the form is mechanically pa. They destroyed about 4 blows of the hammer, and about half of the disc-shaped rod was removed.  Thereafter, the mold was kept in water at room temperature for 30 minutes and then the remnants of the sand disc were removed.  The result was a hollow, aluminum casting with high surface quality on the side of the rod. .  Thus, the examples above illustrate the reality of achieving the objectives of the present invention, improving the adhesion strength of refractory filler particles and preventing the formation of cracks when removing items from a tooling.
    17
    876052
    18 Table 1
    Note:
    Tensile strength after 24 hours, kgf / cm Tensile strength after 30 12.810.97 20 12,011.53
    Table 3 in the numerator is survivability, MHHJ in the denominator is the time before samples are taken from the equipment, min.,. ./ ,/// Table 2 48 h, kgf / cm 12.011, .25 10.699.7
    Continuation of table 3
    no sediment, then sediment appears
    1: 3,4
    1: 3,4
    1: 3.2
    68
    67 65 75
    68
    Continuation of table 4
    after 2 months without sediment, then sediment
    after 1 month without sediment, then sediment
    after 1 month without sediment, then sediment
    after 10 months a precipitate appears
    no sediment at KiepHO after 12 months
    no sediment 12 months
    MINIMUM, 5 months without sediment, up to 6 months sediment
    minimum 10 months without sediment, then sediment
    minimum 2.5 months without sediment, up to 6 months precipitation
    at least 2.5 months without sediment, up to 6 months misfire
    23
    876052
    24
    65 75 68
    67
    65 75
    68
    权利要求:
    Claims (2)
    [1]
    67 65 Claim 1. The mass for the manufacture of casting cores and molds, as well as refractory and abrasive products, including refractory filler and complex. binder based on aluminum phosphate, characterized in that, in order to increase the adhesion strength of the particles of the refractory filler and prevent the formation of cracks when removing products from the tooling, it contains, as a complex binder, borated aluminum phosphate in combination with water and material based on alkaline earth metal oxide bonding with the following ratio of ingredients in wt.%: Refractory filler60, 0-99.5 Complex binder 0, 5-40.0 Moreover, the ingredients of the complex binder, namely borira ny aluminum phosphate in combination with the water and the oxide-based material Ser Neny alkaline earth metal are taken in the following ratio in weight.%: 25,6-87,3 aluminum phosphate borated Voda5,7-6 3.4
    ca without sediment, up to 6 months sediment
    sediment after about 2.5 months
    sediment after about 2.5 months
    minimum 2.5 months without sediment, up to 6 months precipitation
    sediment after about 2.5 months
    Oh oh
    small sediment after about 2.5 months. The material based on an alkaline earth metal oxide compound is 2.6-46.0. At the same time, the boron content in borated aluminum phosphate is 0.08-1.9 wt.% with a weight ratio of phosphorus to total the content of aluminum and boron (1.98: 1) (4.54: 1).
    2. The mass according to claim 1, 6 tons of l and ch ayusch and the fact that as a material based on an oxide compound of an alkaline earth metal, it contains an oxide or hydroxide of an alkaline earth metal. 3. Mass on PP. 2, that is, it contains magnesium oxide as a material based on an alkaline earth metal oxide compound. 4. The mass according to claim 1, which is based on the fact that, as a material based on an oxide compound of an alkaline earth metal, it contains natural chemical compounds of an alkaline earth metal, including oxides along with an alkaline earth metal and its oxide. elements selected from the group of the next series: silicon, aluminum, zirconium boron, titanium.
    [2]
    2587605226
    5. Mass on PP. 1-4, about t of the reading series; silicon, aluminum, wjp — which, as a grade, is boron, titanium, with a weight material based on an oxide compound (2: 1) - (8 si) between an oxide or an alkali earth metal, onahydroxide, an alkaline earth metal, contains silicates, silicones, silicones, to these natural chemical aluminates, zirconates, vorates, titanium, and compounds of alkaline earth metals alkaline earth metals.
    6.Massa gyu p.1, I distinguish-7. Mass on PP. 1-6, about tl looking for the fact that as a matter of fact that the material
    On the basis of an oxide compound based on an alkaline earth metal oxide compound, it contains 0.9–8.5 alkaline-earth oxide or hydroxide on the base metal oxide, a ground metal in combination with a low-temperature
    Native adsorption of nitrogen. earth metal, including sources of information,
    along with alkaline earth metal oxide into account during the examination and its oxide, oxide compounds i. Dmono. J. Japan Foundryman "
    elements selected from the group Barely Sod 1969, 41, 6,415-422.
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    同族专利:
    公开号 | 公开日
    JPS52155130A|1977-12-23|
    AU471979B2|1976-05-13|
    DE2452232A1|1975-05-22|
    DD118239A6|1976-02-20|
    RO67599A|1981-06-30|
    ATA913174A|1977-10-15|
    JPS5326563B2|1978-08-03|
    SE412582B|1980-03-10|
    AU7512474A|1976-05-13|
    FR2250589A2|1975-06-06|
    DE2452232C2|1987-07-02|
    PH10164A|1976-09-13|
    CA1029751A|1978-04-18|
    SE7413108L|1975-05-15|
    IT1022655B|1978-04-20|
    ES431958A1|1977-02-16|
    AT343825B|1978-06-26|
    FR2250589B2|1978-05-19|
    JPS5327208B2|1978-08-07|
    BE822131R|1975-03-03|
    JPS5080220A|1975-06-30|
    BR7409418A|1976-05-18|
    CH603274A5|1978-08-15|
    PL101960B1|1979-02-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2522548A|1946-10-03|1950-09-19|Thoger G Jungersen|Method of making a phosphate gel and mold with phosphate gel binder|US4127157A|1977-03-07|1978-11-28|Ashland Oil, Inc.|Aluminum phosphate binder composition cured with ammonia and amines|
    JPS5831258B2|1979-05-10|1983-07-05|Chuo Hatsumei Kenkyusho Kk|
    DE3604370A1|1986-02-12|1987-08-13|Klein Schanzlin & Becker Ag|Process for producing moulding cores which readily disintegrate|
    DE3931276A1|1989-09-20|1991-03-28|Budenheim Rud A Oetker Chemie|Modelling material for precision casting in dentistry - has powdered crude mixt. contg. quartz, alumina, cristobalite, molten material magnesia, tri:calcium phosphate, bentonite and boric acid|
    GB9022754D0|1990-10-19|1990-12-05|Pilkington Controlled Release|Improvements in or relating to water dispersible moulds|
    DE10311606B3|2003-03-14|2004-12-09|Laempe + Gies Gmbh|Forms and cores containing magnesium sulphate with phosphate / borate additive and their manufacture and use|
    US8579013B2|2011-09-30|2013-11-12|General Electric Company|Casting mold composition with improved detectability for inclusions and method of casting|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/415,852|US3930872A|1973-04-17|1973-11-14|Binder compositions|
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