CN108485328A - A kind of normal temperature cure inorganic coating, preparation method and coated workpieces - Google Patents

Abstract

The present invention provides a kind of normal temperature cure inorganic coating, including component A and B component；The component A includes：The metal phosphate binder of 50~65 parts by weight；The alundum (Al2O3) of 33~42 parts by weight；The phosphate dihydrogen manganese of 2~8 parts by weight；The graphene oxide of 0~2 parts by weight；The B component includes：The silica of 50~65 parts by weight；The high alumina cement of 10~15 parts by weight；The clay powder of 15~25 parts by weight；The magnesia of 8~15 parts by weight；Metal ion in the metal phosphate binder is one or more of aluminium ion, zinc ion, copper ion, iron ion, ferrous ion, calcium ion；The mass ratio of the component A and B component is (4~5)：1；The thickness of the graphene oxide is 4~20nm；The flit size of the graphene oxide is 5~10 μm.The present invention also provides a kind of preparation method of normal temperature cure inorganic coating and a kind of coated workpieces.

Description

A kind of normal temperature curing inorganic coating, its preparation method and coating workpiece

technical field

The invention belongs to the technical field of anti-corrosion materials, and in particular relates to a normal temperature curing inorganic paint, a preparation method thereof and a coated workpiece.

Background technique

As we all know, in today's world, with the continuous development of the world economy, the development and application of metal materials have occupied a considerable proportion, becoming the most widely used engineering materials by human beings. However, pure metal materials have many problems in terms of high temperature oxidation resistance, corrosion resistance, and wear resistance, which seriously restrict their service life and scope of use. Cermet coating combines the dual advantages of metal and ceramics. It not only has the heat resistance, wear resistance and corrosion resistance of ceramic materials, but also has the toughness of metal materials, making it possible for some materials to be used in some special occasions. Thereby broadening the range of material selection and part design.

At present, cermet coatings have been successfully used in aerospace, military, electronics, machinery, chemical and other industries. Among them, the high temperature resistant adhesive ceramic coating is a typical representative of the high temperature resistant protective coating. The stress is small, the cost of surface treatment is low, and the process is simple. More importantly, it can meet the on-site construction requirements in harsh environments, which greatly broadens its promotion and application in large-scale equipment. Chinese patent 201510399025.8 discloses an alkali-resistant ceramic coating material and its preparation method, which can be cured in a wide temperature range, but it is difficult to achieve room temperature curing. Chinese patent 201510807495.3 reports a water-based aluminum-containing phosphate ceramic anti-corrosion coating and its preparation and curing method, which requires a curing temperature of 120°C. The early patent 201310378767.3 disclosed a high temperature resistant room temperature curing phosphate adhesive and its preparation method. This technology provides a useful idea for realizing the room temperature curing of ceramic coatings. Unfortunately, the coating preparation contains chromium oxide, which has great harm to the environment.

In summary, the preparation of the high-temperature-resistant adhesive ceramic coating disclosed in the prior art is basically based on high-temperature curing, and there are still the following problems in industrial application: first, it is difficult to apply to large-scale industrial equipment, and second, the baking process is cumbersome And it consumes time and energy. Third, the chromium oxide added in the coating preparation has great harm to the environment.

Contents of the invention

The object of the present invention is to provide a normal temperature curing inorganic coating, its preparation method and coating workpiece. The inorganic coating in the present invention can be cured at normal temperature without high temperature baking, and has good product performance.

The invention provides a room temperature curing inorganic coating, comprising A component and B component;

The A component includes:

50～65 parts by weight of metal phosphate binder;

33～42 parts by weight of aluminum oxide;

2 to 8 parts by weight of manganese dihydrogen phosphate;

0 to 2 parts by weight of graphene oxide;

The B component includes:

50～65 parts by weight of silicon dioxide;

10-15 parts by weight of high alumina cement;

The clay powder of 15～25 parts by weight;

8～15 parts by weight of magnesium oxide;

The metal ions in the metal phosphate binder are one or more of aluminum ions, zinc ions, copper ions, iron ions, ferrous ions and calcium ions.

The mass ratio of the A component to the B component is (4-5):1.

The thickness of described graphene oxide is 4～20nm;

The microchip size of the graphene oxide is 5-10 μm.

Preferably, the particle size of the aluminum oxide is 20-40 μm.

The invention provides a method for preparing an inorganic coating cured at room temperature, comprising the following steps:

A) mixing metal compound with phosphoric acid solution, heating to obtain metal phosphate binder;

B) After mixing 33 to 42 parts by weight of aluminum oxide, 0 to 2 parts by weight of graphene oxide and 2 to 8 parts by weight of manganese dihydrogen phosphate, ball milling is carried out. After the ball milling is over, place the ball milled mixture for 20 to 30 hours, add 50-65 parts by weight of metal phosphate binder to obtain component A;

The rotating speed of the ball mill is 250～300r/min;

The time of the ball milling is 5～10 hours;

C) mixing 50-65 parts by weight of silicon dioxide, 10-15 parts by weight of high-alumina cement, 15-25 parts by weight of clay powder and 8-15 parts by weight of magnesium oxide to obtain component B;

D) Mix component A and component B to obtain an inorganic coating curable at room temperature.

The invention provides a coated workpiece, comprising a metal substrate and a coating coated on the surface of the metal substrate;

The coating is obtained by curing the above-mentioned room-temperature-curing inorganic coating on the surface of the metal substrate at room temperature.

Preferably, the thickness of the coating is 0.1-0.4 mm.

The invention provides a normal temperature curing inorganic coating, which comprises component A and component B; the component A comprises: 50-65 parts by weight of metal phosphate binder; 33-42 parts by weight of aluminum oxide; 2 to 8 parts by weight of manganese dihydrogen phosphate; 0 to 2 parts by weight of graphene oxide; the B component includes: 50 to 65 parts by weight of silicon dioxide; 10 to 15 parts by weight of high alumina cement; 25 parts by weight of clay powder; 8 to 15 parts by weight of magnesium oxide; the metal ion in the metal phosphate binder is one of aluminum ions, zinc ions, copper ions, iron ions, ferrous ions, and calcium ions. species or several. The mass ratio of the A component to the B component is (4-5):1. The thickness of the graphene oxide is 4-20nm; the size of the micro-sheets of the graphene oxide is 5-10 μm.

The normal-temperature self-curing ceramic paint provided by the invention can self-cure at normal temperature, which greatly saves its cost in industrial practical application, reduces construction difficulty, and broadens its popularization and application in large-scale equipment. The experimental results show that the graphene oxide-enhanced environment-friendly normal temperature self-curing ceramic coating provided by the present invention is coated on the surface of metal components, and the formed wet coating is surface-dry within 1 hour in a room temperature and ventilated environment, hard-dry within 24 hours, and completely dry within 25 days. solidified.

Moreover, the room temperature self-curing ceramic coating provided by the present invention includes manganese dihydrogen phosphate and graphene oxide, which can play a good antirust effect in steel products, thereby greatly increasing the environmental protection effect of graphene oxide prepared by the present invention. Corrosion resistance of self-curing ceramic coatings at room temperature. Under the condition of not destroying the coating, the coating in the present invention has no rust after 100 hours in the salt spray resistance test.

Secondly, the room temperature self-curing ceramic coating provided by the present invention includes graphene oxide. Its special two-dimensional structure and mechanical properties can well reduce the expansion of ceramic cracks, improve the toughness of alumina ceramic materials, and increase the coating base. The bonding strength of the material improves the corrosion resistance of the coating. The coating does not contain toxic elements such as chromium, and is healthy and environmentally friendly.

Furthermore, the graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating provided by the present invention has good compactness, wear resistance and friction reduction, and good corrosion resistance; and the preparation process is simple, the cost is low, and it has wide application prospects.

Detailed ways

The invention provides a normal temperature curing inorganic coating, comprising A component and B component;

The A component includes:

50～65 parts by weight of metal phosphate binder;

33～42 parts by weight of aluminum oxide;

2 to 8 parts by weight of manganese dihydrogen phosphate;

0 to 2 parts by weight of graphene oxide;

The B component includes:

50～65 parts by weight of silicon dioxide;

10-15 parts by weight of high alumina cement;

The clay powder of 15～25 parts by weight;

8～15 parts by weight of magnesium oxide;

The metal ions in the metal phosphate binder are one or more of aluminum ions, zinc ions, copper ions, iron ions, ferrous ions and calcium ions.

The mass ratio of the A component to the B component is (4-5):1.

The thickness of described graphene oxide is 4～20nm;

The microchip size of the graphene oxide is 5-10 μm.

In component A, the metal ions in the metal phosphate binder are one or more of aluminum ions, zinc ions, copper ions, iron ions, ferrous ions, and calcium ions. The metal phosphate binder is prepared by reacting a metal compound and a phosphoric acid solution, and the metal compound is preferably a metal oxide and/or a metal hydroxide. The weight part of the metal phosphate binder is preferably 55-60 parts.

The weight part of the aluminum oxide is preferably 35-40 parts, and the particle size of the aluminum oxide is preferably 20-40 μm, more preferably 25-35 μm.

The parts by weight of the manganese dihydrogen phosphate are preferably 3-7 parts, more preferably 4-6 parts, and most preferably 5 parts.

The weight parts of described graphene oxide is preferably 0.5～1 part; The thickness of described graphene oxide is preferably 4～20nm, more preferably 5～18nm, most preferably 10～15nm; The flake size is preferably 5 to 10 μm, more preferably 6 to 9 μm, most preferably 7 to 8 μm.

In component B, the parts by weight of the silica is preferably 55-60 parts; the parts by weight of the high-alumina cement are preferably 11-14 parts, more preferably 12-13 parts; the clay powder The parts by weight are preferably 18-23 parts, more preferably 20-22 parts; the parts by weight of the magnesium oxide are preferably 10-14 parts, more preferably 12-13 parts.

The mass ratio of the A component to the B component is preferably (4-5):1, more preferably 4.5:1.

The present invention also provides a method for preparing an inorganic coating cured at room temperature, comprising the following steps:

A) mixing metal compound with phosphoric acid solution, heating to obtain metal phosphate binder;

B) Mix 33 to 42 parts by weight of aluminum oxide, 0 to 2 parts by weight of graphene oxide and 2 to 8 parts by weight of manganese dihydrogen phosphate and then perform ball milling. After the ball milling, add 50 to 65 parts by weight of metal Phosphate binder to obtain component A;

C) mixing 50-65 parts by weight of silicon dioxide, 10-15 parts by weight of high-alumina cement, 15-25 parts by weight of clay powder and 8-15 parts by weight of magnesium oxide to obtain component B;

D) Mix component A and component B to obtain an inorganic coating curable at room temperature.

In the present invention, the amount of the raw materials used is consistent with the amount of each raw material mentioned above, and will not be repeated here.

In the present invention, the metal compound is preferably a metal oxide and/or metal hydroxide, and the metal species in the metal compound is preferably one or more of aluminum, zinc, copper, iron, ferrous and calcium. kind. The molar ratio of the phosphorus element in the metal phosphate binder in the A component to the metal element therein is (2.0-4.0):1.

In the present invention, the ball mill preferably adopts a star ball mill for ball milling, the pot body used during ball milling is a ceramic pot, and the balls of the ball milling medium are agate balls. The ball-to-material ratio is preferably (1-4):1, more preferably (2-3):1. The speed setting of the ball mill tank is preferably 250-300r/min, more preferably 260-300r/min, and most preferably 280-300r/min. The forward and reverse directions are alternately operated. The speed of the ball mill turntable is about 1/ 2. The forward and reverse runs alternately every 2 hours, and the total running time is 5 to 10 hours to stop the ball mill, more preferably 6 to 8 hours. After the spherical tank is removed, it needs to be placed for 20 to 30 hours, more preferably 24 to 28 hours, and then take a sample , so that the powder obtained after ball milling has a relaxation process. The phosphate binder is then added and mixed to obtain the A component.

In the present invention, the mixing of the A component and the B component is preferably ultrasonic mixing, and an ultrasonic machine is preferably used to ultrasonically disperse the A component and the B component.

The invention also provides a coated workpiece, comprising a metal substrate and a coating coated on the surface of the metal substrate;

The coating is obtained by curing the above normal temperature curing inorganic coating on the surface of the metal substrate at normal temperature.

The thickness of the coating is preferably 0.1-0.4 mm, more preferably 0.2-0.3 mm.

The metal base is preferably steel; specifically, it may be Q235 steel.

The invention provides a normal temperature curing inorganic coating, which comprises component A and component B; the component A comprises: 50-65 parts by weight of metal phosphate binder; 33-42 parts by weight of aluminum oxide; 2 to 8 parts by weight of manganese dihydrogen phosphate; 0 to 2 parts by weight of graphene oxide; the B component includes: 50 to 65 parts by weight of silicon dioxide; 10 to 15 parts by weight of high alumina cement; 25 parts by weight of clay powder; 8-15 parts by weight of magnesium oxide.

The graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating provided by the invention can self-cure at room temperature, which greatly saves its cost in industrial practical application, reduces the difficulty of construction, and broadens its promotion and application in large-scale equipment. application. The experimental results show that the graphene oxide-enhanced environment-friendly normal temperature self-curing ceramic coating provided by the present invention is coated on the surface of metal components, and the formed wet coating is surface-dry within 1 hour in a room temperature and ventilated environment, hard-dry within 24 hours, and completely dry within 25 days. solidified.

Moreover, the graphene oxide enhanced environment-friendly normal temperature self-curing ceramic coating provided by the present invention includes manganese dihydrogen phosphate, which can play a good antirust effect in steel products, thereby greatly increasing the amount of graphene oxide prepared by the present invention. Enhance the corrosion resistance of environment-friendly room temperature self-curing ceramic coatings.

Secondly, the graphene oxide enhanced environment-friendly room temperature self-curing ceramic coating provided by the present invention includes graphene oxide. Its special two-dimensional structure and mechanical properties can well reduce the expansion of ceramic cracks and improve the toughness of alumina ceramic materials. , while increasing the bonding strength of the coating base material and improving the corrosion resistance of the coating. The coating does not contain toxic elements such as chromium, and is healthy and environmentally friendly.

Furthermore, the graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating provided by the present invention has good compactness, wear resistance and friction reduction, and good corrosion resistance; and the preparation process is simple, the cost is low, and it has wide application prospects.

In order to further illustrate the present invention, a room temperature curing inorganic coating and its preparation method provided by the present invention will be described in detail below in conjunction with examples, but it should not be understood as limiting the protection scope of the present invention.

Example 1

Weigh the powder according to 1 part of graphene oxide, 42 parts of aluminum oxide, and 2 parts of manganese dihydrogen phosphate, ball mill it at 300r/min for 8 hours with a planetary ball mill, then weigh 55 parts of phosphate binder, mix the aggregate with phosphoric acid The salt binder was mixed uniformly and magnetically stirred for 4 hours to obtain the coating A component.

Weigh the powder according to 55 parts of silicon dioxide, 10 parts of high alumina cement, 25 parts of clay powder and 10 parts of magnesium oxide to obtain component B of the coating.

The obtained component A and component B were mixed at a ratio of 4:1, and the mixed liquid was manually stirred evenly, and then ultrasonically dispersed for 1 hour using an ultrasonic instrument to obtain a graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating.

Coat the obtained graphene oxide-reinforced environment-friendly self-curing ceramic coating at room temperature on degreased Q235 steel with a coating thickness of about 0.2mm, and then place the coating under dry and ventilated conditions at room temperature, and the surface will dry within 1 hour , work hard within 24 hours, and conduct a test test after 25 days. The results show that:

High temperature resistance: 1000 degrees Celsius thermal weight loss dehydration does not exceed 5%;

Abrasion resistance: 500 grams at 1000 turns, the loss is 0.085g, and the friction coefficient is 0.5;

Salt spray resistance: without damaging the surface coating, no rust will appear after 100 hours;

Applicable time: 12 hours.

Example 2

Weigh the powder according to 1 part of graphene oxide, 42 parts of aluminum oxide, and 2 parts of manganese dihydrogen phosphate, ball mill it at 300r/min for 8 hours with a planetary ball mill, then weigh 55 parts of phosphate binder, mix the aggregate with phosphoric acid The salt binder was mixed uniformly and magnetically stirred for 4 hours to obtain the coating A component.

Weigh the powder according to 60 parts of silicon dioxide, 10 parts of high alumina cement, 20 parts of clay powder and 10 parts of magnesium oxide to obtain component B of the coating.

The obtained component A and component B were mixed at a ratio of 4.5:1. After the mixed solution was manually stirred evenly, it was ultrasonically dispersed for 1 hour using an ultrasonic instrument to obtain a graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating.

Coat the obtained graphene oxide-reinforced environment-friendly self-curing ceramic coating at room temperature on degreased Q235 steel with a coating thickness of about 0.32 mm, and then place the coating under dry and ventilated conditions at room temperature, and the surface will dry within 1 hour , work hard within 24 hours, and conduct a test test after 25 days. The results show that:

High temperature resistance: 1000 degrees Celsius thermal weight loss dehydration does not exceed 5%;

Abrasion resistance: 500 grams at 1000 turns, the loss is 0.082g, and the friction coefficient is 0.48;

Salt spray resistance: without damaging the surface coating, no rust will appear after 100 hours;

Applicable time: 12 hours.

Example 3

Weigh the powder according to 2 parts of graphene oxide, 41 parts of aluminum oxide, and 2 parts of manganese dihydrogen phosphate, ball mill it at 300r/min for 8h with a planetary ball mill, then weigh 55 parts of phosphate binder, mix the aggregate with phosphoric acid The salt binder was mixed uniformly and magnetically stirred for 4 hours to obtain the coating A component.

Weigh the powder according to 60 parts of silicon dioxide, 10 parts of high alumina cement, 20 parts of clay powder and 10 parts of magnesium oxide to obtain component B of the coating.

The obtained component A and component B were mixed at a ratio of 4.5:1. After the mixed solution was manually stirred evenly, it was ultrasonically dispersed for one hour using an ultrasonic instrument to obtain a graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating.

Coat the obtained graphene oxide-enhanced environment-friendly self-curing ceramic coating at room temperature on degreased Q235 steel with a coating thickness of about 0.42 mm, and then place the coating under dry and ventilated conditions at room temperature, and the surface will dry within 1 hour , work hard within 24 hours, and conduct a test test after 25 days. The results show that:

High temperature resistance: 1000 degrees Celsius thermal weight loss dehydration does not exceed 5%;

Abrasion resistance: 500g at 1000 rpm, loss of 0.080g, friction coefficient of 0.45;

Salt spray resistance: without damaging the surface coating, no rust will appear after 100 hours;

Applicable time: 12 hours.

Example 4

Weigh the powder according to 2 parts of graphene oxide, 41 parts of aluminum oxide, and 2 parts of manganese dihydrogen phosphate, ball mill it at 300r/min for 8h with a planetary ball mill, then weigh 55 parts of phosphate binder, mix the aggregate with phosphoric acid The salt binder was mixed uniformly and magnetically stirred for 4 hours to obtain the coating A component.

Weigh the powder according to 60 parts of silica, 10 parts of high alumina cement, 17 parts of clay powder and 13 parts of magnesium oxide to obtain component B of the coating.

The obtained component A and component B were mixed at a ratio of 5.0:1. After the mixed solution was manually stirred evenly, it was ultrasonically dispersed for one hour using an ultrasonic instrument to obtain a graphene oxide-enhanced environment-friendly room temperature self-curing ceramic coating.

Coat the obtained graphene oxide-reinforced environment-friendly self-curing ceramic coating at room temperature on degreased Q235 steel with a coating thickness of about 0.25 mm, and then place the coating under dry and ventilated conditions at room temperature, and the surface will dry within 1 hour , work hard within 24 hours, and conduct a test test after 25 days. The results show that:

High temperature resistance: 1000 degrees Celsius thermal weight loss dehydration does not exceed 5%;

Abrasion resistance: 1000 turns to 500 grams, the loss is 0.078g, and the friction coefficient is 0.44;

Salt spray resistance: without damaging the surface coating, no rust will appear after 100 hours;

Applicable time: 12 hours.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (5)

1. A room temperature curing inorganic coating, comprising A component and B component; The A component includes: 50～65 parts by weight of metal phosphate binder; 33～42 parts by weight of aluminum oxide; 2 to 8 parts by weight of manganese dihydrogen phosphate; 0 to 2 parts by weight of graphene oxide; The B component includes: 50～65 parts by weight of silicon dioxide; 10-15 parts by weight of high alumina cement; The clay powder of 15～25 parts by weight; 8～15 parts by weight of magnesium oxide; The metal ions in the metal phosphate binder are one or more of aluminum ions, zinc ions, copper ions, iron ions, ferrous ions, and calcium ions; The mass ratio of the A component to the B component is (4-5):1; The thickness of described graphene oxide is 4～20nm; The microchip size of the graphene oxide is 5-10 μm. 2. The room temperature curing inorganic coating according to claim 1, characterized in that the particle size of the aluminum oxide is 20-40 μm. 3. A preparation method for room temperature curing inorganic coating, comprising the following steps: A) mixing metal compound with phosphoric acid solution, heating to obtain metal phosphate binder; B) After mixing 33 to 42 parts by weight of aluminum oxide, 0 to 2 parts by weight of graphene oxide and 2 to 8 parts by weight of manganese dihydrogen phosphate, ball milling is carried out. After the ball milling is over, place the ball milled mixture for 20 to 30 hours, add 50-65 parts by weight of metal phosphate binder to obtain component A; The rotating speed of the ball mill is 250～300r/min; The time of the ball milling is 5～10 hours; C) mixing 50-65 parts by weight of silicon dioxide, 10-15 parts by weight of high-alumina cement, 15-25 parts by weight of clay powder and 8-15 parts by weight of magnesium oxide to obtain component B; D) Mix component A and component B to obtain an inorganic coating curable at room temperature. 4. A coated workpiece, comprising a metal substrate and a coating coated on the surface of the metal substrate; The coating is obtained by curing the normal-temperature-curable inorganic coating according to any one of claims 1-2 or the normal-temperature-curable inorganic coating prepared by the preparation method according to claim 3 on the surface of the metal substrate at room temperature. 5. The coated workpiece according to claim 4, characterized in that, the thickness of the coating is 0.1-0.4 mm.