CN100482861C - Manufacture method of ceramic lining composite square steel tube - Google Patents

Manufacture method of ceramic lining composite square steel tube Download PDF

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Publication number
CN100482861C
CN100482861C CNB2006100476668A CN200610047666A CN100482861C CN 100482861 C CN100482861 C CN 100482861C CN B2006100476668 A CNB2006100476668 A CN B2006100476668A CN 200610047666 A CN200610047666 A CN 200610047666A CN 100482861 C CN100482861 C CN 100482861C
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powder
steel pipe
orders
square steel
thermite
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CN1919786A (en
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王凤辉
焦安源
高兴岐
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Anshan University of Science and Technology
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Abstract

The invention discloses a manufacturing method of ceramic lining composite steel pipe, which comprises the following parts: Fe2O3 powder, Al powder, SiO2 powder and CrO3 powder, wherein these materials are blended evenly to generate the product through toasting, allocating, loading, adding core and igniting; certain shaped core material is added in the middle of square pipe, which reduces quality of thermit to control manufacturing cost; the thermit is added directly in the square steel pipe with external radius less than 35mm to ignite.

Description

Manufacture method of ceramic lining composite square steel tube
Technical field
The present invention relates to a kind of top coat new technical field of steel, particularly is the ceramic-lined composite steel tube production method.
Background technology
Ceramic lining composite square steel tube and manufacture method thereof are to utilize the chemical energy of reactant inside to come synthetic materials.After reactant was lighted, combustion reactions can the oneself be kept, and generally no longer needed supplementing energy.Whole technological process is very simple, and energy consumption is low, production efficiency height, and product purity height.
Ceramic lining composite square steel tube is produced the technological process of ceramic coating: with the Al powder and the Fe of certain particle size 2O 3Powder prepares in proportion, mixes through mixer, in the pipe of packing into, makes it reach certain density, and square steel pipe is vertically placed, the top igniting of thermite.Under the effect of high reaction heat, reaction continues to carry out, and generates Al 2O 3With the melt of Fe, form the molten bath on thermite top.Because sizable density difference, gravity separation takes place in the molten bath, and the Fe that density is big sinks the Al that density is little 2O 3Float on top, molten bath.Because of Al 2O 3The fusing point height, the time that liquid phase stops is short, along with liquid level descends, Al 2O 3Melt and inner wall of metal tube contact site be cooled and solidified and combine with metal pipe-wall at first, forms the ceramic coating liner.Along with reaction interface descends continuously, just form the successive ceramic coating at the steel pipe inwall, form the thick liner aluminum oxide coating layer of 0.7～4mm up to whole tube walls.Fe melt that density is big and unnecessary ceramic melt are discharged from the steel pipe underpunch together, obtain the multiple-unit tube of lined ceramics coating after the cooling.The reaction formula is as follows:
4Fe 2O 3+6Al→3Al 2O 3+3FeO+5Fe
3FeO+2Al→Al 2O 3+3Fe
CrO 3+2Al—→Al 2O 3+Cr+1094KJ
Gravity separation ceramic lining composite square steel tube technology is to come from self propagating high temperature to synthesize, and makes it to separate by action of gravity, obtains required product, and the distinguishing feature of this method is that the synthetic cost of material is low, the production efficiency height.Currently utilize this technology to prepare compound coating mainly to concentrate on preparation circle composite steel tube.The technology that generates ceramic coating on non-round tube inwall and the sheet material has wide application prospect, but does not also have maturation in the prior art.
Chinese patent CN 1226451C has announced a kind of manufacturing process of ceramic composite steel pipe but has mainly concentrated on the compound round steel pipe of preparation.It is as follows that pipe and square tube prepare the difference that ceramic-lined coating exists: 1. proportioning, pack density, grain weight matrix are than, SiO 2And CrO 3Factors such as additive influence the rule basically identical to the two, but because the shape difference of steel pipe matrix, so mobile better when square steel pipe requires to be in molten state, the preparation of reagent is different from round steel pipe like this.When 2. preparing the ceramic-lined coating of square tube, place, four right angles coating of square tube is thicker, and the tube wall place is thinner relatively.If just cause the tube wall place to come off easily when the thickness difference of the two is big than shallow layer, thus for reagent select materials, prescription and treatment process aspect also with round steel pipe difference to some extent.If 3. the developmental tube placement is not vertically, then generally can only cause the coat-thickness inequality for pipe, square tube is then twisted easily, is out of shape, and each plane coat-thickness inequality has produced uneven stress simultaneously, causes ceramic coating to come off easily.
Summary of the invention
At prior art problems, the purpose of this invention is to provide a kind of gravity separation self propagating high temperature synthetic technology of utilizing that satisfies working conditions such as high temperature, low impact and produce the method for ceramic lining composite square steel tube, and obtain ceramic-lined composite sheet by cutting steel pipe side, this matrix material satisfies the needs of product to structure properties (intensity, toughness etc.) and environmental performance (wear-resisting, anti-corrosion, high temperature resistant etc.) simultaneously, can be widely used in every field such as metallurgy, mine, chemical industry, electric power.
For achieving the above object, technical solution of the present invention is described below:
A kind of manufacture method of ceramic lining composite square steel tube, raw material comprises Fe 2O 3Powder, Al powder, SiO 2Powder and CrO 3Powder is characterized in that this method may further comprise the steps:
1) the steel pipe matrix is prepared: the cutting test square steel pipe, with the oxide skin on hydrochloric acid flush away surface, clean the back at a distance dry from electric furnace, and back to be dried is clean with the inwall polishing with sand paper;
2) select materials: with 100-300 purpose sieve raw material is screened, then raw material is carried out drying respectively, with loft drier to Fe 2O 3Powder and SiO 2Powder carried out 140 ℃ of freeze-day with constant temperature 24 hours respectively in automatically controlled thermostat container, the Al powder carries out drying under 60 ℃, detected behind the no moisture standby;
3) batching: the preparation thermite, thermite is according to following recipe configuration, by weight percentage; Mixing raw material mixed 12 hours with blender;
Fe 2O 3Powder 100 orders～300 orders 65%～70%;
Al powder 100 orders～300 orders 20%～30%;
SiO 2Powder 100 orders～300 orders 2%～8%;
CrO 3Powder 100 orders～300 orders 1%～4%;
4) join core: grown up in the outside and carry out the processing that inside adds core in the square tube of 35mm, what core adopted is square steel pipe, and the size of its external diameter depends on the steel pipe matrix;
5) charging: the thermite that mixes, according to the grain weight matrix than 2～5.5g/cm 3Principle and the thickness of the pottery that obtains of the expectation weight of determining raw material, thermite evenly is filled in the space of steel pipe and core body, keep the vertical state of steel pipe simultaneously;
6) light the reagent tubulation: light thermite, it is reacted, under the effect of high reaction heat, reaction continues to carry out, and generates Al 2O 3With the melt of Fe, form the molten bath on thermite top; Along with reaction interface descends continuously, form the successive ceramic coating at the steel pipe inwall, form the thick liner aluminum oxide coating layer of 1～3mm up to whole tube walls, promptly obtain ceramic lining composite square steel tube after the cooling.
The manufacture method of ceramic lining composite square steel tube of the present invention compared with prior art, its novelty and creativeness are embodied in:
(1) temperature of combustion is high, is generally 2000 ℃～3000 ℃.Low melting point impurity when building-up reactions in the starting material can volatilize effusion, product purity and quality height.
(2) building-up process has experienced great thermograde, may occur defective in the resultant and concentrate and non-equilibrium phase, and product is active high, can obtain mutually complicated and metastable phase.
(3) the industrial production operation is few, required equipment is simple, the place is little, with short production cycle.Production technique is simple, and synthetic reaction process is rapid, generally finishes in seconds or tens of seconds, saves the process time.
(4) energy-saving benefit is obvious, and the solid combustion synthetic technology relies on the chemical reaction between the reactive material to generate compound, and discharges a large amount of heat energy.It is different with traditional metallurgical methods such as interior melting of stove or sintering, does not need external energy, therefore, can save a large amount of energy, and techno-economic effect is very remarkable.
(5) the synthetic materials scope that can prepare is wide especially, is suitable for making the ceramic lining composite square steel tube of multiple caliber, multiple thickness.
(6) synthetic coating, because the result of high-temperature fusant and high temperature action, ceramic layer and matrix are realized mechanical bond and little metallurgical binding, in conjunction with tight; Ceramic layer has certain toughness, can bear low impact loading.The coating that some high thermopositive reaction forms can produce metallurgical binding.The ceramic metal composite square steel tube of preparation can improve significantly that it is high temperature resistant, high abrasion, high anti-corrosion capability.
Description of drawings
Fig. 1 is the experiment device schematic diagram of Ceramic Composite small cross-section square steel pipe.
Fig. 2 is the experiment device schematic diagram of Ceramic Composite large section square steel pipe.
Fig. 3 is for preparing successful ceramic lining composite square steel tube.
The composition board that Fig. 4 obtains by the compound square tube of cutting.
Among Fig. 1, Fig. 2,1-magnesium powder 2-square steel pipe 3-thermite 4-fiber board 5-base 6-fuse 7-gripping unit
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.The present invention is based on that the principle of thermite reaction realizes:
4Fe 2O 3+6Al→3Al 2O 3+3FeO+5Fe
3FeO+2Al→Al 2O 3+3Fe
Figure C200610047666D00051
A kind of manufacture method of ceramic lining composite square steel tube, raw material comprises Fe 2O 3Powder, Al powder, SiO 2Powder and CrO 3Powder, this method may further comprise the steps:
1) the steel pipe matrix is prepared: cutting test reaches the length that needs with square steel pipe, with the oxide skin on hydrochloric acid flush away surface, cleans after drying, and back to be dried is clean with the inwall polishing with sand paper;
2) select materials: with 100-300 purpose sieve raw material is screened, then raw material is carried out drying respectively, with loft drier to Fe 2O 3Powder and SiO 2Powder carried out 140 ℃ of freeze-day with constant temperature 24 hours respectively in automatically controlled thermostat container, the Al powder carries out drying under 60 ℃, detected behind the no moisture standby;
3) batching: the preparation thermite, thermite is according to following recipe configuration, by weight percentage; Mixing raw material mixed 12 hours with blender;
Fe 2O 3Powder 100 orders～300 orders 65%～70%;
Al powder 100 orders～300 orders 20%～30%;
SiO 2Powder 100 orders～300 orders 2%～8%;
CrO 3Powder 100 orders～300 orders 1%～4%.
4) join core:
Utilize the inventive method to prepare the ceramic-lined coating of large section square tube, the square steel pipe of external diameter more than 35mm need be in the middle core material that add definite shape of square tube, reduce the quality of thermite, to reduce the heat that self-propagating reaction produces, prevent that matrix from burning leakage, the control production cost.For the square steel pipe of external diameter less than 35mm, its inner chamber is directly put into thermite, lights to get final product.In experiment, the core material of selecting for use is a square steel pipe.When adopting square steel or round steel, can the purity of melt not exerted an influence.Core surface also can generate ceramic coating in reaction process, but because iron is bigger with the difference of thermal expansion coefficients of pottery, after the cooling, ceramic coating and core material can produce the slit of 0.5～1.0mm, knocking the back coating can come off from core surface fully, and core material can be reused.We have studied the two kinds of shape-square steel pipes or the round steel pipe of core material, and its dimensional parameters comprises length h, the outer cross section length of side C of square steel pipe 1Or cylinder steel pipe outside radius C 2Length h equals or is slightly larger than square tube length to get final product.Parameters C 1, C 2Calculate by following formula:
C 1 = ( a - 2 d ) 2 - v × a ρ × h
C 2 = 1 3.14 [ ( a - 2 d ) 2 - v × a ρ × h ]
In the formula: the outer length of side of a-square tube, cm;
The d-wall thickness, cm;
V-matrix volume, cm 3
ρ-binder density, g/cm 3, get 1.4～2.5 usually;
α-grain weight matrix ratio, the ratio of thermite quality and steel pipe volume is got 2～5.5g/cm usually 3
The h-square tube length, cm.
What fuse volume of the present invention was selected the reasons are as follows:
-1. the size of fuse has directly had influence on the amount of filling reagent, and the thickness of ceramic coating that generates at most of reagent is big comparatively speaking, and the thickness that reagent generates ceramic coating less is little, so at first will select according to the thickness of ceramic coating that expectation obtains.2. should to make grain weight matrix ratio be 2～5.5g/cm to the amount of reagent 3
5) charging: the thermite that mixes, according to 1.4-2.5g/cm 3Packing density be filled in the steel pipe and (, skirt and sheet asbestos fixed) for the reaction that skirt is arranged, note keeping the vertical state of steel pipe simultaneously.If transformer and hot-wire ignition are adopted in igniting, then should bury resistance wire on the reaction reagent top, adjust the output voltage and the electric current of transformer.The resistance wire diameter that adopts is 0.5mm, and the transformer output voltage is 24V, and outward current is 1～2A, about the general about 30s of ignition delay time.If adopt the magnesium powder to light, only need sprinkle the small amount of magnesium powder, then with the magnesium ribbon magnesium powder that ignites in the thermite mid-way.
6) light the reagent tubulation: light thermite, make it according to 2Al+Fe 2O 3→ Al 2O 3+ 2Fe+836KJ reacts, and under the effect of high reaction heat, reaction continues to carry out, and generates Al 2O 3With the melt of Fe, form the molten bath on thermite top.Because sizable density difference, gravity separation takes place in the molten bath, and the Fe that density is big sinks the Al that density is little 2O 3Float on top, molten bath.Because of Al 2O 3The fusing point height, the time that liquid phase stops is short, along with liquid level descends, Al 2O 3Melt and inner wall of metal tube contact site be cooled and solidified and combine with metal pipe-wall at first, forms the ceramic coating liner.Along with reaction interface descends continuously, just form the successive ceramic coating at the steel pipe inwall, form the thick liner aluminum oxide coating layer of 1～3mm up to whole tube walls.Fe melt that density is big and unnecessary ceramic melt are discharged from the steel pipe underpunch together, obtain ceramic lining composite square steel tube after the cooling.
With aforesaid method length of side 20-60mm outside, wall thickness 1.5-4mm, length is to have made ceramic lining composite square steel tube on a series of square steel pipes of 70-350mm.The thickness of its ceramic layer is 0.8-3.5mm.
The ceramic-lined laminar surface that generates is uniform and smooth, does not have significantly visible pore, crackle and bulge.Composite ceramic coat sample, its structure are the outer metallic matrix layer that is, internal layer is the lining coating of preparation.Obviously contain two class materials in the liner, class is the white metal of particulate state or reunion shape, is metal or intermetallic compound phase; Another kind of gray and do not have metalluster is ceramic phase.Alumina-ceramic and iron liquid melt can't form metallurgical binding, pottery and the mechanical bond mode of metallic matrix based on the banding formula.Hardness value is more than 1200～1400 (HV0.2).Ceramic layer is organized mainly by α-Al 2O 3Matrix phase and FeOAl 2O 3Spinel mutually constitute SiO 2In pottery, mainly exist with spinel English phase structure.
Below be the specific embodiment that the contriver provides, the invention is not restricted to these embodiment.
Embodiment 1:
Matrix is the square steel pipe of 30 * 30 * 1.5mm, and length is 200mm.
Adopting Al powder degree is 200 ± 20 orders, Fe 2O 3Granularity 150～250 orders, SiO 2Granularity 200 ± 20 orders, packing density are 1.5～2.0g/cm 3, the grain weight matrix is than 3.0～5.5g/cm 3, the ratio of reagent is Al: Fe 2O 3SiO 2=24.2%: 71.8%: 4%.
Normal-temperature reaction, naturally cooling, generate thickness evenly, smooth surface, thickness be about the pottery of 1.5-2.5mm, the average hardness hardness value reaches as high as 1415 (HV0.2) at 1200～1400 (HV0.2).It is firm that pottery combines with metallic matrix, difficult drop-off.
Embodiment 2:
Matrix is the square steel pipe of 30 * 30 * 1.5mm, and length is 200mm.
Adopting Al powder degree is the 100-200 order, Fe 2O 3Granularity 100～200 orders, SiO 2Granularity 100-200 order, CrO 3Powder degree 100-200 order, packing density is 1.5～2.0g/cm 3, the grain weight matrix is than 3.0～5.5g/cm 3, the ratio of reagent is Al: Fe 2O 3: SiO 2: CrO 3=26%: 68%: 4%: 2%.
Normal-temperature reaction, naturally cooling, generate thickness evenly, smooth surface, thickness be about the pottery of 1.5-2.5mm, the average hardness hardness value reaches as high as 1415 (HV0.2) at 1200～1400 (HV0.2).It is firm that pottery combines with metallic matrix, difficult drop-off.
Embodiment 3::
Matrix is 60 * 60 * 4mm square steel pipe, and length is 100mm, and material is Q235.
Adopting Al powder degree is the 100-200 order, Fe 2O 3Granularity 100～200 orders, SiO 2Granularity 100-200 order, packing density 1.4～1.8g/cm 3, the grain weight matrix is than 3.0～5.5g/cm 3, the ratio of reagent is Al: Fe 2O 3: SiO 2=30%: 66%: 4%.
In the experiment of preparation large section Ceramic Composite square tube,, added SiO in the thermite in order to improve the ceramic layer density 2, because it has double influence to coating quality, we have determined rational SiO 2Addition 4%.Fuse is the round steel pipe of Φ 30mm, normal-temperature reaction, naturally cooling.Prepared smooth surface, the uniform Ceramic Composite square tube of coat-thickness sample, can directly use; Also can be cut into the Ceramic Composite steel plate, be a kind of effective ways of new preparation surface of steel plate ceramic composite coating.
Matrix material constitutes by three layers, steel pipe layer promptly, based on the intermediate layer and the inboard ceramic layer of iron particle, wherein air retaining wall thickness (being made up of intermediate layer and ceramic layer) is between 1.0～3.5mm, transition layer and base layer do not have obvious bonding interface, and be clear with ceramic bonding interface.Alumina-ceramic and iron liquid melt can't form metallurgical binding, and wetting reaction can not take place, thereby form the combination based on the machinery fixing.
The present invention has passed through test of many times, and above-mentioned prescription can be enumerated a lot of embodiment, and the present invention does not enumerate one by one, as long as can prepare ceramic lining composite square steel tube in scope of the present invention.

Claims (3)

1, a kind of manufacture method of ceramic lining composite square steel tube, raw material comprises Fe 2O 3Powder, Al powder, SiO 2Powder and CrO 3Powder is characterized in that this method may further comprise the steps:
1) the steel pipe matrix is prepared: the cutting test square steel pipe, with the oxide skin on hydrochloric acid flush away surface, clean the back at a distance dry from electric furnace, and back to be dried is clean with the inwall polishing with sand paper;
2) select materials: with 100-300 purpose sieve raw material is screened, then raw material is carried out drying respectively, with loft drier to Fe 2O 3Powder and SiO 2Powder carried out 140 ℃ of freeze-day with constant temperature 24 hours respectively in automatically controlled thermostat container, the Al powder carries out drying under 60 ℃, detected behind the no moisture standby;
3) batching: the preparation thermite, thermite is according to following recipe configuration, by weight percentage; Mixing raw material mixed 12 hours with blender;
Fe 2O 3Powder 100 orders～300 orders 65%～70%;
Al powder 100 orders～300 orders 20%～30%;
SiO 2Powder 100 orders～300 orders 2%～8%;
CrO 3Powder 100 orders～300 orders 1%～4%;
4) join core: grown up in the outside and carry out the processing that inside adds core in the square tube of 35mm, what core adopted is square steel pipe, and the size of its external diameter depends on the steel pipe matrix;
5) charging: the thermite that mixes, according to the grain weight matrix than 2～5.5g/cm 3, thermite evenly is filled in the space of steel pipe and core body, keep the vertical state of steel pipe simultaneously;
6) light the reagent tubulation: light thermite, it is reacted, under the effect of high reaction heat, reaction continues to carry out, and generates Al 2O 3With the melt of Fe, form the molten bath on thermite top; Along with reaction interface descends continuously, form the successive ceramic coating at the steel pipe inwall, form the thick liner aluminum oxide coating layer of 1～3mm up to whole tube walls, promptly obtain ceramic lining composite square steel tube after the cooling.
2, a kind of manufacture method of ceramic lining composite square steel tube according to claim 1, it is characterized in that adopting Al powder degree is the 100-200 order, Fe 2O 3Granularity 100～200 orders, SiO 2Granularity 100-200 order, CrO 3Powder degree 100-200 order, packing density is 1.5～2.0g/cm 3, the grain weight matrix is than 3.0～5.5g/cm 3, the ratio of thermite is Al:Fe 2O 3: SiO 2: CrO 3=26%:68%:4%:2%.
3, the ceramic lining composite square steel tube of method manufacturing according to claim 1 and 2, it is characterized in that with aforesaid method length of side 20-60mm outside, wall thickness 1.5-4mm, length is to have made ceramic lining composite square steel tube on a series of square steel pipes of 70-350mm, and the thickness of its ceramic layer is 0.8-3.5mm.
CNB2006100476668A 2006-09-08 2006-09-08 Manufacture method of ceramic lining composite square steel tube Expired - Fee Related CN100482861C (en)

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