CN105964891B - A kind of phosphate inorganic adhesive sand with high fluidity and preparation method thereof - Google Patents
A kind of phosphate inorganic adhesive sand with high fluidity and preparation method thereof Download PDFInfo
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- CN105964891B CN105964891B CN201610339000.3A CN201610339000A CN105964891B CN 105964891 B CN105964891 B CN 105964891B CN 201610339000 A CN201610339000 A CN 201610339000A CN 105964891 B CN105964891 B CN 105964891B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/185—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents containing phosphates, phosphoric acids or its derivatives
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Abstract
The invention belongs to casting field, and in particular to a kind of phosphate inorganic adhesive sand with high fluidity and preparation method thereof.Each component quality parts ratio is burning sand 2500, phosphate inorganic adhesive 100, metal oxide curing agent 8, additive 5 in the present invention, additive includes the solution as made from the nonionic surface active agent such as one or more of APGs, l 61, l 62, S 80, MOA 9P, the granularity mixed with the solution is the silica of the mesh of 400 mesh~1200, and the weight proportion of the nonionic surface active agent and silica is 1：5~1：3.The present invention retain the intrinsic clean environment firendly of phosphate binders sand, the advantage such as collapsibility is good, intensity is higher while, the mobility of phosphate binders sand is greatly improved, meets the novel green mold material and casting method of modern Foundry Production.
Description
Technical field
The invention belongs to casting field, and in particular to a kind of phosphate inorganic adhesive sand and its system with high fluidity
Preparation Method.
Background technology
Casting is one of fundamental technology of modern mechanical manufacturing industry, as the important component of Chinese manufacturing, I
State's casting industry is also in development at full speed, however, in the industry, problem of environmental pollution is always a large amount of existing, with
Everybody environmental consciousness steps up, and it is the key for realizing Green foundry to develop Green foundry process and material.But at present,
Still large batch of during castings production to use organic resin binding agent, such binding agent, which typically contains furans, benzene, phenol etc., to be had
Noxious material, pollution can be all produced in each production links such as moulding, coremaking, cast and old sand processing, discharges a large amount of toxic gases.
Waterglass turns into the most possible founding materials for realizing Green foundry production requirement as another inorganic binder, but black
Non-ferrous metal casting collapsibility is poor, and regenerating used is big to energy demand, and integrated cost is higher.
The existing phosphate inorganic adhesive sand developed has the advantages that environmental pollution is small, intensity is high, collapsibility is good,
Become a kind of very promising founding materials.But current phosphate inorganic adhesive is in Foundry Production, due to phosphate without
Boric acid is added in machine binding agent as modifying agent, the viscosity of binding agent to increase, and causes the flowing of former phosphate inorganic adhesive sand
Property it is poor so that the phosphate inorganic adhesive sand degree of packing is inadequate in modeling process, cause produce cast part age rate it is low and cast
Part is second-rate, it is difficult to adapt to high-volume, high efficient production precision casting mold, the demand of core in modern Foundry Production.
The content of the invention
The present invention reaches raising phosphate binders sand flow and moved by adding additive in phosphate inorganic adhesive sand
The purpose of property.
To reach above-mentioned purpose, base case provided by the invention is the phosphate inorganic adhesive for having high fluidity
Sand, including burn sand, phosphate inorganic adhesive, curing agent and additive, each component mass fraction for burn sand 2500, phosphate without
Machine binding agent 100, curing agent 8, additive 5；
Phosphate inorganic adhesive includes aluminium hydroxide, phosphoric acid, boric acid, citric acid and water, and each component percentage by weight is
Aluminium hydroxide 8%~12%, phosphatase 24 6%~50%, boric acid 3%~6%, citric acid 2%~4%, water 30%~34%, institute
The degree of neutralization for stating phosphate inorganic adhesive is 3.6：1~4：1, the concentration of the phosphoric acid is 70%；
Curing agent is magnesia, aluminum oxide, zinc oxide, iron oxide, calcium oxide, cupric oxide, can be a kind of with single use,
It is a variety of that addition can be mixed；
Additive includes being lived by the non-ionic surface such as one or more of APGs, l-61, l-62, S-80, MOA-9P
Property solution made from agent, the granularity mixed with the solution is the silica of the mesh of 400 mesh~1200, and the non-ionic surface is lived
Property agent and silica weight proportion be 1：5~1：3.
The sand fluidity that the concentration of phosphoric acid makes when being 70% is best, if concentration is 85% phosphoric acid, can make
The mobility of molding sand declines 60%；Additive is the main material as increase sand fluidity.Through experiment test, with other gold
Category oxide is compared, and when zinc oxide is as curing agent, the room temperature tensile intensity of phosphate inorganic adhesive sand is larger.Nonionic table
Face activating agent is soluble in water not to be dissociated, and is not existed in the form of an ion in the solution, is not easy the shadow by acid, alkali and strong electrolyte
Ring, so its stability is higher, suitable use here, and cationic surfactant, anion surfactant
For stability it is poor, it is impossible to reach the demand of experiment, select nonionic surfactant herein.
The preferred scheme 1 that improvement to base case obtains：The nonionic surfactant is l-61.
The preferred scheme 2 that improvement to base case obtains：The weight of the nonionic surface active agent and silica
Amount proportioning is 1：4；Obtained sand fluidity is optimal under the proportioning.
The preferred scheme 3 that improvement to base case either preferred scheme 1 or preferred scheme 2 obtains：The phosphate
The degree of neutralization of inorganic binder is 3.8：1；Through experimental test, degree of neutralization 3.8：When 1, obtained sand bond is bigger.Reason
Synthesis for aluminate or phosphate inorganic binder is the reaction according to aluminium hydroxide and phosphoric acid：
Al(OH)3+3H3PO4=Al (H2PO4)3+3H2O (1)
2Al(OH)3+3H3PO4=Al2(HPO4)3+6H2O (2)
Al(OH)3+H3PO4=AlPO4+3H2O (3)
Main component is Al (H in the aluminum phosphate solution of synthesis2PO4)3, also Al2(HPO4)3, it is also possible to have a small amount of
AlPO4, degree of neutralization 3.8：When 1, regulation has obtained more suitable Al (H2PO4)3And Al2(HPO4)3Ratio, make intensity ratio
The binding agent of other degree of neutralization has large increase.
The preferred scheme 4 that improvement to base case either preferred scheme 1 or preferred scheme 2 obtains：The phosphate
Inorganic binder each component percentage by weight is aluminium hydroxide 11%, phosphatase 24 9%, boric acid 4%, citric acid 3%, water 33%.
The preferred scheme 5 that the improvement of preferred scheme 3 obtains：The granularity of the silica is 600 mesh.
The preferred scheme 6 that the improvement of preferred scheme 5 obtains：The making temperature of phosphate inorganic adhesive is 110~130
℃。
Present invention also offers the preparation method of the phosphate inorganic adhesive sand with high fluidity, specifically include as follows
Step：
Following material all using the metering method of mass fraction,
The first step, phosphate inorganic adhesive is prepared,
First 14 parts of aluminium hydroxides and 26 parts of water are added in container, magnetic stirrer is started, heating apparatus temperature is adjusted
Container is heated for 120 DEG C, when fluid temperature is at 98 DEG C~100 DEG C, it is 70% that 100 parts of concentration are then added into container
Phosphoric acid, continue to be heated to solution clarification, now 106 DEG C~108 DEG C of solution temperature, keeping temperature, are then slowly added into 8 parts of boron
Acid, react to solution to become and clarify, add 5 parts of citric acids, solution is again after secondary clearing, you can stop heating, close agitator, treat
Solution naturally cools to room temperature, that is, phosphate inorganic adhesive is made；
Second step, additive preparation,
1 part of non-ionic surfactant l-61 wiring solution-forming is first taken, by above-mentioned solution and dioxy that 4 parts of granularities are 600 mesh
SiClx is by obtained additive after uniformly mixing；
Second step, sand processed,
First by additive with 50/100 burning sand be first well mixed, be well mixed after gained mixture again with curing agent zinc oxide
Uniformly mixing, is added followed by phosphate inorganic adhesive and is well mixed, and mixes 3~4min, you can shake out.If added material compared with
More, then the mulling time can increase by 1~2min, but the time may not exceed 6min, if because overlong time, obtained sand and puddle mixer
Between frictional heat, cause obtained sand to start to solidify in advance, influence intensity.
Beneficial effects of the present invention are：Retain the intrinsic clean environment firendly of phosphate binders sand, collapsibility be good, intensity compared with
While high advantage, the mobility of phosphate binders sand is greatly improved, meets the novel green of modern Foundry Production
Mold material and casting method.Additive is added during mulling, the mobility of phosphate inorganic adhesive sand can be made have pole
Big to improve, concrete principle is that the molecular structure feature of the surfactant in additive has asymmetry for it, be by with
Hydrophilic polar group and the organic compound that there is the non-polar group of hydrophobicity to be formed, 600 mesh preparing spherical SiO 2s
It can then be filled in the space that 50/100 mesh burns sand, surfactant be overlayed on 600 mesh preparing spherical SiO 2s so that surface
Activating agent can be mixed preferably with sand, and the polar group of surfactant, away from water, is coated on to dampening rather than polar group
Sand surface, ball-shaped micro powder, which is filled in space, makes sand be easier to slide, and this additive will not cause very big shadow to intensity
Ring.Therefore by additive come to greatly improve the mobility of phosphate inorganic adhesive sand be extraordinary selection.
Embodiment
In order to preferably explain the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
First 14 parts of aluminium hydroxides and 26 parts of water are added in container, magnetic stirrer is started, heating apparatus temperature is adjusted
Container is heated for 120 DEG C, when fluid temperature is at 98 DEG C~100 DEG C, it is 70% that 100 parts of concentration are then added into container
Phosphoric acid, continue to be heated to solution clarification, now 106 DEG C~108 DEG C of solution temperature, keeping temperature, are then slowly added into 8 parts of boron
Acid, react to solution went clear, add 5 parts of citric acids, solution is again after secondary clearing, you can stop heating, close agitator, treat
Solution naturally cools to room temperature, i.e., obtained phosphate inorganic adhesive, each component weight in obtained phosphate inorganic adhesive
Percentage is aluminium hydroxide 11%, concentration is 70% phosphatase 24 9%, boric acid 4%, citric acid 3%, water 33%；
1 part of l-61 is taken to be configured to solution after being mixed by a certain percentage with water, then it is 600 mesh that the solution is added into 4 parts of granularities
Silica additive is made；
2g additives are burnt into sand with 1000g50/100 first uniformly to mix, well mixed rear gained mixture is consolidated with 3.2g again
Agent zinc oxide uniformly mixes, and is added followed by 40g phosphate inorganic adhesive mixing 3.5min, after being well mixed, using hammer
Striking examines the mobility of phosphate inorganic adhesive sand, and sample mobility reaches 6.06g；Made on SAC paddle type mill sampling machines
" 8 " word calibrated bolck sample is some, and then using being come out of the stove after the heating baking oven 23min that temperature is 155 DEG C, the room temperature tensile of gained is strong
Spend for 1.90MPa.
Embodiment 2
In the case where experimental method is constant, the composition ratio of the data of changing section experiment material, i.e. a change additive
Example, when making additive, after taking 1 part of l-61 to be mixed by a certain percentage with water, add the titanium dioxide that 3 parts of granularities are 600 mesh
Additive is made in silicon；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 5.96g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.92MPa.
Embodiment 3
In the case where experimental method is constant, the composition ratio of the data of changing section experiment material, i.e. a change additive
Example, when making additive, after taking 1 part of l-61 to be mixed by a certain percentage with water, add the titanium dioxide that 5 parts of granularities are 600 mesh
Additive is made in silicon；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 6.05g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.81MPa.
Embodiment 4
In the case where experimental method is constant, the composition of the data of changing section experiment material, i.e. a change additive,
When making additive, after taking 1 part of l-61 to be mixed by a certain percentage with water, add 4 parts of granularities and be made up of the silica of 400 mesh
Additive；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 6.01g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.91MPa.
Embodiment 5
In the case where experimental method is constant, the composition of the data of changing section experiment material, i.e. a change additive,
When making additive, after taking 1 part of l-61 to be mixed by a certain percentage with water, add 4 parts of granularities and be made up of the silica of 800 mesh
Additive；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 5.32g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.89MPa.
Embodiment 6
In the case where experimental method is constant, the composition of the data of changing section experiment material, i.e. a change additive,
When making additive, after taking 1 part of APG to be mixed by a certain percentage with water, the silica that 4 parts of granularities are 600 mesh is added
Additive is made；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 5.02g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.91MPa.
Embodiment 7
In the case where experimental method is constant, the composition of the data of changing section experiment material, i.e. a change additive,
When making additive, after taking 1 part of MOA-9P to be mixed by a certain percentage with water, the silica system that 4 parts of granularities are 600 mesh is added
Into additive；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 5.95g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.89MPa.
Embodiment 8
In the case where experimental method is constant, the data of changing section experiment material, i.e., curing agent zinc oxide is changed to oxygen
Change magnesium；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 6.05g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.81MPa.
Embodiment 9
In the case where experimental method is constant, the data of changing section experiment material, i.e., curing agent zinc oxide is changed to oxygen
Change calcium；
The mobility of phosphate inorganic adhesive sand is examined using hammering method, sample mobility reaches 6.05g；Hammered in SAC
It is some that " 8 " word calibrated bolck sample is made on formula sampling machine, then using temperature to be come out of the stove after 155 DEG C of heating baking oven 23min, institute
The room temperature tensile intensity obtained is 1.79MPa.
First group of experiment：Embodiment 1, embodiment 2, embodiment 3, according to control variate method, adjust l-61 and silica
Ratio, the ratio for drawing surfactant and silica is 1：Mobility is best when 4.
| Proportioning mode (weight ratio) | Mobility (g) | Intensity (MPa) |
| 1：3 | 5.96 | 1.92 |
| 1：4 | 6.06 | 1.90 |
| 1：5 | 6.05 | 1.81 |
Second group of experiment：Embodiment 1, embodiment 4, embodiment 5, according to control variate method, the ratio of l-61 and silica
Example is constant, changes the mesh number of silica, when silica is 600 mesh, mobility is more preferable.
3rd group of experiment：Embodiment 1, embodiment 6, embodiment 7, according to control variate method, surfactant and titanium dioxide
The constant rate of silicon, when surfactant selects, mobility is more preferable.
| Surfactant | Mobility (g) | Intensity (MPa) |
| APG | 5.02 | 1.91 |
| l‐61 | 6.06 | 1.90 |
| MOA-9P | 5.95 | 1.89 |
4th group of experiment：Embodiment 1, embodiment 8, embodiment 9, according to control variate method, change curing agent, selective oxidation
When zinc is as curing agent, mobility is more preferable.
| Curing agent | Mobility (g) | Intensity (MPa) |
| Magnesia | 6.05 | 1.81 |
| Zinc oxide | 6.06 | 1.90 |
| Calcium oxide | 6.05 | 1.79 |
Embodiment 1 is the preferred plan of the phosphate inorganic adhesive sand of preparation high fluidity, mobility highest, and intensity
It is larger.
The general principle of the present invention has been shown and described above.It should be understood by those skilled in the art that the present invention not by
Merely illustrating the principles of the invention described in the limitation of above-described embodiment, above-described embodiment and specification, this hair is not being departed from
On the premise of bright spirit and scope, various changes and modifications of the present invention are possible, and these changes and improvements both fall within claimed
The scope of the invention in.The scope of protection required by this application should be based on the content of the claims, specific in specification
The records such as embodiment can be used for the content for explaining claim.
Claims (8)
1. a kind of phosphate inorganic adhesive sand with high fluidity, it is characterised in that including burning sand, phosphate inorganic bonds
Agent, curing agent and additive, each component mass fraction are burning sand 2500, phosphate inorganic adhesive 100, curing agent 8, additive
5；
The phosphate inorganic adhesive includes aluminium hydroxide, phosphoric acid, boric acid, citric acid and water, and each component percentage by weight is
Aluminium hydroxide 8%~12%, phosphatase 24 6%~50%, boric acid 3%~6%, citric acid 2%~4%, water 30%~34%, the phosphate without
The degree of neutralization of machine binding agent is 3.6：1~4：1, the concentration of the phosphoric acid is 70%；
The curing agent is the one or more in magnesia, aluminum oxide, zinc oxide, iron oxide, calcium oxide, cupric oxide；
The additive is included by one or more of APGs, l-61, l-62, S-80, MOA-9P non-ionic surfactant
Solution made from agent, the granularity mixed with the solution are the silica of the mesh of 400 mesh~1200, the non-ionic surfactant
The weight proportion of agent and silica is 1：5~1：3.
2. the phosphate inorganic adhesive sand according to claim 1 with high fluidity, it is characterised in that：It is described it is non-from
Subtype surfactant is l-61.
3. the phosphate inorganic adhesive sand according to claim 1 with high fluidity, it is characterised in that：It is described it is non-from
The weight proportion of subtype surfactant and silica is 1：4.
4. the phosphate inorganic adhesive sand with high fluidity according to claim 1 or 2 or 3, it is characterised in that：Institute
The degree of neutralization for stating phosphate inorganic adhesive is 3.8：1.
5. the phosphate inorganic adhesive sand with high fluidity according to claim 1 or 2 or 3, it is characterised in that：Institute
Phosphate inorganic adhesive each component percentage by weight is stated as aluminium hydroxide 11%, phosphatase 24 9%, boric acid 4%, citric acid 3%, water
33%。
6. the phosphate inorganic adhesive sand according to claim 4 with high fluidity, it is characterised in that：The dioxy
The granularity of SiClx is 600 mesh.
7. the phosphate inorganic adhesive sand according to claim 6 with high fluidity, it is characterised in that：The phosphoric acid
The making temperature of salt inorganic binder is 110~130 DEG C.
8. the preparation method of the phosphate inorganic adhesive sand according to claim 1 with high fluidity, its feature exist
In comprising the following steps that：
Following material all using the metering method of mass fraction,
The first step, phosphate inorganic adhesive is prepared,
First 14 parts of aluminium hydroxides and 26 parts of water are added in container, start magnetic stirrer, heating apparatus temperature is adjusted to 120
DEG C container is heated, when fluid temperature is at 98 DEG C~100 DEG C, the phosphoric acid that 100 parts of concentration are 70% is then added into container,
Continue to be heated to solution clarification, now 106 DEG C~108 DEG C of solution temperature, keeping temperature, are then slowly added into 8 parts of boric acid, reaction
Clarified to solution change, add 5 parts of citric acids, solution is again after secondary clearing, you can stopped heating, close agitator, treat solution certainly
Room temperature so is cooled to, that is, phosphate inorganic adhesive is made；
Second step, additive preparation,
1 part of nonionic surface active agent l-61 wiring solution-forming is first taken, by above-mentioned solution and titanium dioxide that 4 parts of granularities are 600 mesh
Additive is made after uniformly mixing in silicon；
3rd step, sand processed,
Additive first is burnt into sand with 50/100 mesh to be first well mixed, gained mixture is equal with curing agent zinc oxide again after being well mixed
Even mixing, it is added followed by phosphate inorganic adhesive and is well mixed, mixes 3~4min, you can shake out.
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| CN114535499B (en) * | 2021-12-31 | 2023-06-02 | 北京航空航天大学宁波创新研究院 | Moisture absorption resistant inorganic binder powder for casting, activating solution and using method |
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Address after: 400709 No. 6 Wuxing Middle Road, Tongjiaxi Town, Beibei District, Chongqing Patentee after: Chongqing Changjiang moulding material (Group) Limited by Share Ltd Address before: 401320 Fengqi Road, Caijiagang Town, Beibei District, Chongqing Patentee before: Chongqing Changjiang moulding material (Group) Limited by Share Ltd |