CN114709022A - Flame-retardant ceramizable silicone rubber sheath cable and preparation method thereof - Google Patents
Flame-retardant ceramizable silicone rubber sheath cable and preparation method thereof Download PDFInfo
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- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
- H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
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Abstract
The invention relates to a flame-retardant ceramifiable silicon rubber sheath cable and a preparation method thereof, the flame-retardant ceramifiable silicon rubber sheath cable comprises a conductor, wherein the conductor is sequentially provided with a middle protective layer and a flame-retardant ceramifiable silicon rubber sheath from an inner layer to an outer layer, and the flame-retardant ceramifiable silicon rubber sheath comprises the following components in parts by weight: 100 parts of raw silicon rubber, 5-25 parts of white carbon black, 1-10 parts of vulcanizing agent, 20-400 parts of ceramic powder and 0-100 parts of ceramic forming auxiliary agent; the ceramizable powder comprises the following components in parts by weight: 5-120 parts of glass powder, 5-20 parts of muscovite, 5-200 parts of magnesium hydroxide, 5-200 parts of aluminum hydroxide, 1-20 parts of iron oxide and 1-20 parts of phenyl silicone oil; the molar ratio of Mg, Al and Si in the magnesium hydroxide, the aluminum hydroxide and the silicon rubber crude rubber is as follows: 0.4-0.6: 1: 2-5. The flame-retardant ceramifiable silicon rubber sheath cable can quickly form a firm ceramifiable shell when being burnt at high temperature, and has excellent ceramifiable, fireproof, heat-insulating and machinable properties.
Description
Technical Field
The invention relates to a flame-retardant ceramic silicone rubber sheathed cable and a preparation method thereof, belonging to the technical field of cable material preparation.
Background
In recent years, the occurrence rate of fire disasters is high nationwide, and the electric line fault is one of the main causes of accidents. The failure reasons include: using non-flame-retardant wires and cables, damage of wires and cables, faults of wire and cable joints, insulation aging of wires and cables and the like. The frequent occurrence of cable safety accidents has resulted in a plurality of serious casualty events, which poses a non-negligible threat to the safety of the public. In the technical fields of mines, nuclear power stations, ship manufacturing and the like, cables are a serious problem, and once the technology does not reach the standard, irrecoverable results can be caused at any time. Similarly, in the civil application, especially in high-rise buildings, supermarkets, hospitals, large public entertainment places, rail transit facilities and other densely populated places, the quality performance of cables is more closely related to the safety of people's lives and properties.
At present, the market occupies the dominant position of common cables with weak protection facilities, and most of the cables currently in use still have no flame retardant and fireproof performance. When a fire occurs, the burning of the cable is accompanied by various dangers such as electric leakage, combustion supporting, toxic gas generation and the like, and the spreading of fire can be promoted. This undoubtedly increases the difficulty of fire fighting work, and also amounts to burying a further timed bomb for life rescue.
At present, most of the fire-resistant insulated cables put into use in the market are magnesium oxide mineral fire-resistant insulated cables and fire-resistant cables wound by mica tapes, and generally have good high-temperature resistance and combustion resistance. The magnesium oxide mineral fireproof insulated cable has the disadvantages that the magnesium oxide mineral fireproof insulated cable is difficult to lay and install, the cost of raw materials is high, and the magnesium oxide mineral fireproof insulated cable is difficult to popularize and use on a large scale; the fire-resistant cable wound by the mica tape needs to be wound in multiple layers in the production process, and the working procedure is heavy and complicated. Meanwhile, due to the level of a manufacturing process, the lap joint of the fire-resistant cable wound by the mica tape is easy to have defects, and the mica tape becomes thin and brittle and is easy to fall off after a fire disaster occurs, so that the fire-resistant effect is poor. Therefore, neither is an optimal fire resistant insulated cable. In contrast, other flame retardant cable performance levels are also less than ideal and are difficult to meet with higher technical requirements and long term stable maintenance. On the other hand, the safety awareness of the cables of the people needs to be improved, the requirements for the cables are generally low, potential safety hazards are easily ignored, and the protection is not in time when a fire disaster happens. In summary, there is a need for a more advanced and excellent flame retardant cable to fill the gap in the field of domestic and foreign safety cables. Under the policy of continuously promoting the electricity utilization safety of China, the safety requirements of wires and cables in the future civil field are continuously improved, and the requirements of flame-retardant and fire-resistant wires and cables are continuously improved. At present, the flame-retardant ceramic silicon rubber material only opens partial markets at home, the application range of the flame-retardant ceramic silicon rubber material is yet to be further expanded, and the flame-retardant ceramic silicon rubber material has considerable development space under the support of national policies.
Based on the mechanism of ceramic formation of the flame-retardant ceramic-containing silicone rubber, the performance of the similar ceramic-containing silicone rubber cable can be judged. The silicone rubber can be decomposed at high temperature to produce SiO2And eutectic reaction is carried out with the fused ceramic filler/fluxing agent system to form the ceramic body. XRD test is carried out on the sintered sample, and only amorphous SiO is generated after verification2In the case of (2), the ceramic body cannot meet the high strength requirement. However, although flame-retardant ceramifiable rubber cables on the market have a certain output, the ceramifiable silicon rubber with an obvious new XRD peak after calcination is still in a few. Therefore, higher technical barriers need to be overcome, the ceramization performance needs to be optimized, a ceramizable silicon rubber sheath cable capable of generating a new XRD peak after calcination is researched and developed, the flame retardant and ceramic performance is remarkably improved, and the method has important significance.
Disclosure of Invention
Aiming at the defects of the existing flame-retardant and fire-resistant cable, the invention provides a flame-retardant ceramic silicon rubber sheath cable and a preparation method thereof, which are used in the fields of high-end cables and civil cables. The internal structure of the cable is the same as that of a conventional cable, and the outer sheath uses special ceramic silicon rubber filler. The cable has excellent flame retardant and ceramic forming performances, can form a circle of hard and firm ceramic body outside the cable during high-temperature calcination, protects the cable from dripping, melting, short circuit and disconnection, is impact-resistant and high-temperature and high-pressure resistant, thereby greatly reducing the possibility of fire caused by the fire of the cable, timely ensuring the smoothness of electric power and communication when the fire happens, and being beneficial to restraining the spread of fire and preventing the concurrence of electric power accidents.
Summary of The Invention
According to the flame-retardant ceramic-capable silicone rubber sheathed cable provided by the invention, when a fire disaster occurs, silicone rubber serving as a sheathed material and inorganic filler interact to form a compact ceramic layer under the action of a ceramic forming auxiliary agent, and an obvious crystallization peak appears in an XRD spectrogram, which shows that the ceramic-capable silicone rubber outer sheath generates obvious ceramic forming conversion during calcination, so that a new ceramic phase is generated. The ceramifiable silicon rubber cable is small in volume change rate and high in hardness after being calcined at high temperature early, and shows excellent high-temperature resistance; low smoke, no halogen and green, and meets the national highest standard requirement.
Detailed Description
The technical scheme of the invention is as follows:
the flame-retardant ceramifiable silicon rubber sheath cable comprises a conductor, wherein a middle protective layer and a flame-retardant ceramifiable silicon rubber sheath are sequentially arranged from an inner layer to an outer layer of the conductor, and the flame-retardant ceramifiable silicon rubber sheath comprises the following components in parts by weight:
100 parts of raw silicon rubber, 5-25 parts of white carbon black, 1-10 parts of vulcanizing agent, 20-400 parts of ceramic powder and 0-100 parts of ceramic forming auxiliary agent;
the ceramifiable powder comprises the following components in parts by weight: 5-120 parts of glass powder, 5-20 parts of muscovite, 5-200 parts of magnesium hydroxide, 5-200 parts of aluminum hydroxide, 1-20 parts of iron oxide and 1-20 parts of phenyl silicone oil;
further limiting the molar ratio of the magnesium hydroxide, the aluminum hydroxide and the Mg, Al and Si in the raw silicon rubber in the components as follows: 0.4-0.6: 1: 2-5.
According to the invention, the raw silicone rubber is preferably a blend system of various raw silicone rubbers and raw silicone rubbers with other materials, including peroxide type hot vulcanized raw silicone rubbers, addition type hot vulcanized raw silicone rubbers, condensation type room temperature vulcanized raw silicone rubbers, addition type room temperature vulcanized raw silicone rubbers and blend systems of the four types of raw silicone rubber compounds with other materials.
According to the invention, the raw silicone rubber is preferably peroxide type raw heat-vulcanized silicone rubber or addition type raw heat-vulcanized silicone rubber.
According to the present invention, it is preferable that the vulcanizing agent is a vulcanizing agent used for normally vulcanizing the raw silicone rubber, and the vulcanizing agent is different according to the kind of the raw silicone rubber, for example, the vulcanizing agent used for the peroxide type heat vulcanized raw silicone rubber is bis-2, 4, bis-2, 5, BPO, etc., and the vulcanizing agent used for the addition type vulcanized raw silicone rubber is a chloroplatinic acid series compound.
According to the invention, preferably, the ceramifiable powder is compounded according to the formula disclosed by the invention; further preferably, in the composition of the ceramifiable powder, the molar ratio of the two elements of Mg and Al is as follows: 0.45-0.55: 1.
According to the invention, preferably, the molar ratio of the magnesium hydroxide, the aluminum hydroxide and the three elements of Mg, Al and Si in the raw silicone rubber in the flame-retardant ceramic-capable silicone rubber sheath is as follows: 0.45-0.55: 1: 2-5.
According to the invention, preferably, the white carbon black composition is 10-20 parts. The addition of the white carbon black can obviously improve the mechanical property of the silicone rubber.
According to the invention, in the preferable composition of the ceramizable powder, the preferable composition of the phenyl silicone oil is 1-10 parts. The phenyl silicone oil has good high temperature resistance and flame resistance, can improve the ignition point of the silicone rubber to a certain extent as an additive, and can be self-extinguished after ignition.
According to the invention, preferably, the ceramic forming auxiliary agent is a boron compound, and further preferably boric acid, zinc borate and sodium borate; most preferred is zinc borate;
preferably, the addition amount of the ceramic forming aid is preferably 1 to 50 parts, and more preferably 1 to 30 parts.
According to the invention, the flame-retardant ceramic-able silicone rubber sheath component preferably further comprises other fillers or auxiliaries, wherein the other fillers or auxiliaries are various additives which enhance or do not significantly reduce the performance of the silicone rubber, and the additives comprise a thermal oxygen stabilizer, a flame retardant, a foaming agent, a deep curing agent, a pigment, a plasticizer and the like.
According to the invention, the material of the flame-retardant ceramic silicon rubber sheath is prepared by the following method:
uniformly mixing raw silicon rubber, white carbon black, ceramifiable powder and a ceramic assistant, adding a vulcanizing agent, and vulcanizing to obtain the silicon rubber ceramic.
According to the present invention, preferably, the intermediate protective layer further comprises, in order from the inner layer to the outer layer: an insulating layer and an inner protective layer;
further preferably, the insulating layer and the inner sheath layer are made of cross-linked polyvinyl chloride (XLPVC) or Polyethylene (PVC), and have good heat resistance, oxidation resistance and flame retardance. The middle protective layer and the flame-retardant ceramic silicon rubber sheath jointly protect the internal components, and the thickness is determined according to the requirement. The cable with the middle protective layer only comprising the insulating layer and the inner protective layer can be used as a flexible fireproof cable.
According to the invention, preferably, for medium-low voltage fire-resistant cables, automobile cables and emergency power cables, the middle protective layer is positioned between the insulating layer and the inner protective layer, and the filling layer and the belting layer are sequentially arranged, wherein the filling layer is adjacent to the insulating layer. Preferably, the belting layer is an alkali-free fiberglass cloth belting layer, and the filling layer is a high-flame-retardant polyethylene layer.
According to the invention, preferably, for cables which need to bear large mechanical pressure, the intermediate protective layer further comprises an armor layer arranged at the outermost layer of the intermediate protective layer. The armor can further support inner structure, improves the shockproof compressive capacity of cable. Preferably, the armor is a steel wire armor.
According to the invention, preferably, when the cable is a mine flame-retardant fire-resistant cable, the middle protective layer further comprises an inner shielding layer, an outer shielding layer, a fire-resistant layer and an oxygen isolation layer, wherein the two insulating layers are respectively a first insulating layer and a second insulating layer; the middle protective layer comprises an inner layer and an outer layer in sequence: the inner shield layer, the first insulating layer, the outer shield layer, the second insulating layer, the filling layer, the belting layer, the flame retardant coating separates the oxygen layer, interior sheath, the armor.
According to the invention, the preparation of the flame-retardant ceramic silicon rubber sheath adopts a cold extrusion process, the temperature of a screw, a machine head and a machine body of an extruder is lower than 40 ℃, the highest temperature of the screw, the machine head and the machine body is not more than 50 ℃, and the lower the cooling water temperature is, the better the cooling water temperature is;
preferably, the preparation steps are as follows:
(1) opening cooling water of the extruder, cleaning a feeding port and a screw, starting feeding rubber after confirming that no sundries or other rubber exists, ensuring uniform feeding to ensure uniform extrusion, and adopting a forced feeding device, namely a side compression roller, if necessary;
(2) adjusting eccentricity and starting extrusion; the speed is slowed down when the extrusion is started, and then the speed can be slowly increased;
(3) after the eccentricity is adjusted, closing the pipeline seal, and opening steam with the steam pressure of 0.1-0.12 MPa; the pipeline steam can not exceed 0.12MPa, otherwise, the sizing material is easy to self-cure and block the machine head;
(4) the proper specifications of the die core and the die sleeve, the distance between the die core and the die sleeve and the extrusion pressure are adjusted to match the traction speed and the extrusion speed, so that the rough extrusion surface is prevented.
According to the invention, the preparation method of the flame-retardant ceramic-contained silicone rubber sheathed cable comprises the following steps:
respectively carrying out conductor monofilament drawing, monofilament annealing, conductor stranding, insulation extrusion, cabling and adding an intermediate protective layer; and finally, coating the flame-retardant ceramic silicon rubber sheath on the surface of the cable.
According to the present invention, the conductor is preferably made of a conductive material such as copper or aluminum.
The invention has the following technical characteristics and excellent effects:
the flame-retardant ceramic silicon rubber sheath is a novel self-developed high-molecular refractory material, and is prepared by adding a flame-retardant auxiliary agent, a ceramic filler, a fluxing agent, a cross-linking agent and other auxiliary agents in a certain proportion into raw silicon rubber and performing vulcanization and cross-linking. Under the action of a ceramic assistant boron compound, the three elements of Mg, Al and Si can generate MgAl just when the silicon rubber is calcined at high temperature2Si4O12And (4) crystallizing. When the molar ratio of the Mg, the Al and the Si in the ceramifiable silicon rubber is within the range of 0.4-0.6: 1: 2-5, the generated crystallization peak is obvious, and the sinter has the characteristics of high hardness and small volume change rate. A slight excess of Mg element generally produces magnesium oxide. A slight excess of Al element generally produces meta-aluminates. When the contents of the two structures are small (namely, the molar ratio of the Mg to the Al is slightly deviated from 0.5: 1), the two structures have little influence on the ceramic performance of the ceramifiable silicon rubber; however, when the contents of these two structures are large, the hardness of the sintered body is low because the force between the different inorganic phases is weak. Therefore, the moles of both Mg and Al elementsThe ratio is controlled to be 0.4-0.6: 1. The flame-retardant ceramic silicon rubber sheath accurately limits the proportion of the three elements of Mg, Al and Si in the formula, and ensures that the silicon rubber can generate a large amount of MgAl after high-temperature calcination2Si4O12Crystallizing to make the sinter have higher hardness, and realizing the conversion from 'rubber' to 'ceramic'. The hard ceramic layer produced after the ceramic silicon rubber is burnt has stable structure, obvious XRD crystallization peak and good compactness, can not generate obvious cracks, has adhesive force, can wrap the outer layer of the burnt object, and can prevent the further burning of flame, isolate the escape of cracked volatile matters and protect the burnt object from being damaged by big fire.
When exposed to an open flame, the silicone rubber sheath first acts as a flame retardant, and as the temperature and fire rise and become uncontrollable, the sheath can sinter into a hard ceramic, i.e., ceramming occurs, and the degree of hardness is proportional to the temperature and burn time. The hard ceramic shell can form a protective layer for the cable, not only can prevent flame from dropping, but also can keep the integrity of a cable passage, and meets the national regulation GB/T19666-2019 fire-retardant and fire-resistant wire and cable rule, and reaches and exceeds the highest QC-T standard of the current country. The cable outer sheath is compact and firm in structure, weather-proof, high-low temperature resistant, ozone resistant and corona arc resistant, can support cable internal fillers, protect internal conductors and protect external insulation like common cable sheath materials, can play good fireproof and flame-retardant performances when a fire disaster happens, guarantees the smoothness of electric power and communication, and provides reliable guarantee for fire fighting and self rescue.
The flame-retardant ceramifiable silicon rubber sheathed cable can quickly form a firm ceramifiable shell when being burnt at high temperature, an obvious crystallization peak appears through XRD detection, and the ceramifiable strength reaches the standard requirement. The silicon rubber has excellent ceramic, fire-resistant, fireproof, temperature-insulating and machinable performances, low smoke, zero halogen and no toxicity, and has good flexibility and elasticity of silicon rubber, simple laying, time saving and labor saving in normal use. When a fire disaster happens, the ceramic forming performance of the cable can well coat the conductor structure in the hard shell, so that the penetration and the dripping of flame are prevented, and the guarantee is provided for the normal operation of power facilities and power communication. Meanwhile, the ceramic shell is resistant to high-pressure impact, and is not broken by a high-pressure water gun in the fire rescue process to cause dangers such as electric leakage and the like, so that personal safety is fully guaranteed, and more valuable time for escaping is provided.
Drawings
Fig. 1 is a schematic structural diagram of a main body of a flame-retardant ceramifiable silicone rubber sheathed cable according to embodiment 1 of the present invention.
Fig. 2 is a schematic cross-sectional structure view of a flame-retardant ceramifiable silicone rubber sheathed cable according to embodiment 5 of the present invention.
Fig. 3 is a photograph of the flame-retardant ceramifiable silicone rubber samples of comparative example 3, example 1 and comparative example 1 in the test examples at room temperature before calcination.
FIG. 4 is a photograph of the flame retardant ceramifiable silicone rubber samples of comparative example 3, example 1 and comparative example 1 in the test examples after calcination at 800 ℃.
FIG. 5 is an XRD pattern of a sample of the flame retardant ceramifiable silicone rubber of comparative example 3 after calcination at 800 ℃ in the test example.
Fig. 6 is an XRD pattern of the flame-retardant ceramifiable silicone rubber sample of example 1 after calcination at 800 ℃ in the experimental example.
FIG. 7 is an XRD pattern of a sample of the flame retardant ceramifiable silicone rubber of comparative example 1 after calcination at 800 ℃ in the test example.
Wherein: 1. conductor, 2, middle protective layer, 201, insulating layer, 2011, first insulating layer, 2012, second insulating layer, 202, filling layer, 203, belting layer, 204, inner sheath, 205, armor, 206, inner shield, outer shield 207, 208, flame retardant coating, 209, separate the oxygen layer, 3, fire-retardant ceramifiable silicon rubber sheath.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The starting materials used in the examples are either conventional commercially available starting materials or are synthesized according to the literature methods.
Examples 1 to 3
As shown in fig. 1, the flame-retardant ceramifiable silicon rubber sheath cable comprises a conductor 1, wherein the conductor 1 is sequentially provided with a middle protective layer 2 and a flame-retardant ceramifiable silicon rubber sheath 3 from an inner layer to an outer layer, and the middle protective layer 2 sequentially comprises an insulating layer 201, a filling layer 202, a belting layer 203, an inner protective layer 204 and an armor layer 205 from the inner layer to the outer layer;
the conductor 1 is made of copper, the insulating layer 201 and the inner sheath 204 are made of cross-linked polyvinyl chloride (XLPVC), the belting layer 203 is made of alkali-free glass fiber cloth, the armor layer 205 is steel wire armor, and the filling layer 202 is a high-flame-retardant polyethylene layer. The middle protective layer 2 and the flame-retardant ceramic silicon rubber sheath 3 jointly protect the internal components.
The components and the compositions of the raw materials for preparing the flame-retardant ceramifiable silicon rubber sheath 3 are shown in table 1.
The flame-retardant ceramifiable silicon rubber is prepared by the following method:
mixing raw silicon rubber, white carbon black, ceramifiable powder and a ceramic auxiliary agent uniformly on a machine, adding a vulcanizing agent, and vulcanizing according to the type characteristics of the organic silicon rubber compound.
Wherein: the raw silicon rubber is peroxide type hot vulcanized silicon rubber compound, addition type hot vulcanized silicon rubber compound or addition type room temperature vulcanized silicon rubber compound, when the organic silicon rubber compound is peroxide type hot vulcanized silicon rubber, the used vulcanizing agent is double-2, 4, double-2, 5 or BPO, and when the organic silicon rubber compound is addition type vulcanized silicon rubber, the used vulcanizing agent is chloroplatinic acid series compound.
TABLE 1 formulation and ceramifiable Properties of ceramifiable Silicone rubber
Description of the drawings: the No. 1 crude rubber is methyl vinyl silicone rubber crude rubber, the molecular weight is 70 ten thousand, and the vinyl content is 0.23%; the 2# crude rubber is methyl vinyl silicone rubber crude rubber, the molecular weight is 10 ten thousand, and the vinyl content is 0.30%; the No. 1 vulcanizing agent is a double 2,4 vulcanizing agent; the 2# vulcanizing agent is a chloroplatinic acid vulcanizing agent.
The preparation of the flame-retardant ceramifiable silicone rubber sheath described in the embodiment 1-3 adopts a cold extrusion process, wherein the temperature of a screw, a machine head and a machine body of an extruder is lower than 40 ℃, the highest temperature is not higher than 50 ℃, and the lower the cooling water temperature is, the better the cooling water temperature is;
the preparation steps are as follows:
(1) opening cooling water of the extruder, cleaning a feeding port and a screw, starting feeding rubber after confirming that no sundries or other rubber exists, ensuring uniform feeding to ensure uniform extrusion, and adopting a forced feeding device, namely a side compression roller, if necessary;
(2) adjusting eccentricity and starting extrusion; the speed is slowed down when the extrusion is started, and then the speed can be slowly increased;
(3) after the eccentricity is adjusted, closing the pipeline seal, and opening steam with the steam pressure of 0.1-0.12 MPa; the pipeline steam can not exceed 0.12MPa, otherwise, the sizing material is easy to self-cure and block the machine head;
(4) the proper specifications of the die core and the die sleeve, the distance between the die core and the die sleeve and the extrusion pressure are adjusted to match the traction speed and the extrusion speed, so that the rough extrusion surface is prevented.
The method of making the flame retardant ceramifiable silicone rubber sheathed cable of embodiments 1-3, comprising the steps of:
respectively drawing a single wire of the conductor 1, annealing the single wire, stranding the conductor 1, extruding in an insulating way, cabling and adding an intermediate protective layer 2; and finally, coating the flame-retardant ceramic silicon rubber sheath 3 on the surface of the cable.
Example 4
The utility model provides a fire-retardant ceramization silicon rubber sheath cable, includes conductor 1, conductor 1 has set gradually middle inoxidizing coating 2 and fire-retardant ceramization silicon rubber sheath 3 by inlayer to the skin, middle inoxidizing coating 2 only include insulating layer 201 and interior sheath 205, middle inoxidizing coating 2 is insulating layer 201 and interior sheath 205 by inlayer to the skin in proper order. The cable can be used as a flexible fireproof cable.
In this embodiment, the conductor 1 is made of copper, and the insulating layer 201 and the inner sheath 205 are made of cross-linked polyvinyl chloride (XLPVC). The raw materials for preparing the flame-retardant ceramifiable silicon rubber sheath 3 are the same as those in example 2.
The preparation of the flame-retardant ceramifiable silicone rubber sheath 3 and the preparation process of the flame-retardant ceramifiable silicone rubber sheath cable in the embodiment are the same as those in the embodiments 1-3.
Example 5
As shown in fig. 2, the flame-retardant ceramifiable silicon rubber sheath cable comprises a conductor 1, wherein an intermediate protective layer 2 and a flame-retardant ceramifiable silicon rubber sheath 3 are sequentially arranged from an inner layer to an outer layer of the conductor 1,
the middle protective layer 2 comprises the following layers from the inner layer to the outer layer in sequence: the inner shielding layer 206, the first insulating layer 2011, the outer shielding layer 207, the second insulating layer 2012, the filling layer 202, the belting layer 203, the fire-resistant layer 208, the oxygen barrier 209, the inner protective layer 204 and the armor layer 205. The cable can be used as a flame-retardant and fire-resistant cable for mines.
The materials of the conductor 1, the first insulating layer 2011, the second insulating layer 2012, the inner sheath 204, the filler layer 202 and the armor layer 205 described in this embodiment are the same as those of embodiments 1 to 3, and the raw materials for preparing the flame-retardant ceramifiable silicone rubber sheath 3 are the same as those of embodiment 2.
The inner shielding layer 206 is an aluminum foil shielding material, the outer shielding layer 207 is a tinned copper mesh braid, the fire-resistant layer 208 is a mica tape, and the oxygen barrier layer 209 is an alkali-free glass ribbon.
The preparation of the flame-retardant ceramifiable silicone rubber sheath 3 and the preparation process of the flame-retardant ceramifiable silicone rubber sheath cable in the embodiment are the same as those in the embodiments 1-3.
Comparative examples 1 to 3
Comparative examples 1-3 were prepared in the same manner as in example 1, and the composition is shown in Table 1.
Test examples
As shown in fig. 3, the comparative example 3 sample, the example 1 sample, and the comparative example 1 sample are photographs at room temperature from left to right in this order. Photographs of the three samples after calcination at 800 ℃ are shown in FIG. 4.
As can be seen from fig. 4, the sample of example 1 shows ceramic forming performance and small volume change rate after high temperature calcination, the sample of comparative example 3 shows surface notches after calcination, and the sample of example 1 shows stone-like morphology after calcination. While comparative example 1 turned into a crushed residue after high temperature calcination and had no ceramic forming properties.
The XRD patterns of the comparative example 3 sample, the example 1 sample and the comparative example 1 sample after calcination at 800 ℃ were measured as shown in fig. 5, 6 and 7, respectively. Wherein:
FIG. 5 is an XRD pattern of the sample of comparative example 3 after calcination at 800 deg.C, and it can be seen that a distinct XRD crystalline peak appears in the calcined sample, while SiO in the sample2The diffraction peak of (A) is very obvious;
FIG. 6 is the XRD pattern of the sample of example 1 after calcination at 800 deg.C, and it can be seen that the XRD crystalline peaks are particularly pronounced in the calcined sample (in contrast to SiO @)2Less pronounced) and further analysis of the XRD peaks revealed that the peaks corresponded to MgAl2Si4O12Crystallization, which indicates that SiO is present in this sample due to the formation of a large amount of new silicate inorganic phase2Are connected with each other, thereby having better ceramic performance;
FIG. 7 is an XRD pattern of the sample of comparative example 1 after calcination at 800 deg.C, and it can be seen that this sample had only SiO after calcination2No crystalline peak. This explains why the sinter of the sample of comparative example 1 was broken after calcination.
The performance test result shows that the ceramifiable silicon rubber has good ceramifiable performance. Compared with the existing ceramic silicon rubber, the formula of the ceramic silicon rubber has the advantages that the volume change rate of the residue after high-temperature calcination is small, the hardness is high, and an obvious crystallization peak is shown in an XRD test. The flame-retardant ceramifiable silicon rubber sheath cable can quickly form a firm ceramifiable shell when being burnt at high temperature, an obvious crystallization peak appears through XRD detection, and the ceramifiable strength reaches the standard requirement. The ceramic fireproof heat-insulating brick has excellent ceramic, fireproof, heat-insulating and machinable performances, low smoke, zero halogen and no toxicity, is simple and convenient to lay, is suitable for various fields of mining industry, shipbuilding industry, high-end buildings, large-scale public occasions and the like, and has outstanding safety, economical efficiency and practicability.
Claims (10)
1. The utility model provides a fire-retardant can ceramic silicon rubber sheath cable which characterized in that, this fire-retardant can ceramic silicon rubber sheath cable includes the conductor, the conductor has set gradually middle inoxidizing coating and fire-retardant can ceramic silicon rubber sheath by inlayer to skin, fire-retardant can ceramic silicon rubber sheath include the following part by weight component and constitute:
100 parts of raw silicon rubber, 5-25 parts of white carbon black, 1-10 parts of vulcanizing agent, 20-400 parts of ceramic powder and 0-100 parts of ceramic forming auxiliary agent;
the ceramifiable powder comprises the following components in parts by weight: 5-120 parts of glass powder, 5-20 parts of muscovite, 5-200 parts of magnesium hydroxide, 5-200 parts of aluminum hydroxide, 1-20 parts of iron oxide and 1-20 parts of phenyl silicone oil;
the molar ratio of Mg, Al and Si in the magnesium hydroxide, the aluminum hydroxide and the raw silicon rubber is as follows: 0.4-0.6: 1: 2-5.
2. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 1, wherein the raw silicone rubber is various raw silicone rubber or a blending system of raw silicone rubber and other materials, preferably peroxide type heat-vulcanized silicone rubber, addition type heat-vulcanized silicone rubber, condensation type room temperature vulcanized silicone rubber, addition type room temperature vulcanized silicone rubber or a blending system of the four types of silicone rubber and other materials.
3. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 1, wherein the vulcanizing agent is a vulcanizing agent used for normally vulcanizing a raw silicone rubber; preferably, the vulcanizing agent used for the peroxide type heat vulcanized silicone rubber raw rubber is bis-2, 4, bis-2, 5 or BPO, and the vulcanizing agent used for the addition type heat vulcanized silicone rubber raw rubber is a chloroplatinic acid series compound.
4. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 1, wherein the white carbon black is comprised of 10 to 20 parts;
preferably, the composition of the ceramifiable powder comprises 1-10 parts of phenyl silicone oil.
5. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 1, wherein the ceramic forming auxiliary is a boron compound, preferably boric acid, zinc borate, sodium borate;
preferably, the addition amount of the ceramic forming aid is 1-50 parts.
6. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 1, wherein the intermediate protective layer further comprises, in order from the inner layer to the outer layer: an insulating layer and an inner sheath layer;
preferably, the material of the insulating layer and the inner protective layer is cross-linked polyvinyl chloride (XLPVC) or Polyethylene (PVC).
7. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 6, wherein the intermediate protective layer is disposed between the insulating layer and the inner protective layer, and a filling layer and a belting layer are sequentially disposed, the filling layer being adjacent to the insulating layer;
preferably, the belting layer is an alkali-free fiberglass cloth belting layer, and the filling layer is a high-flame-retardant polyethylene layer.
8. The flame retardant ceramifiable silicone rubber-sheathed cable according to claim 7, wherein the intermediate protective layer further comprises an armor layer disposed on an outermost layer of the intermediate protective layer.
9. The flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 8, wherein the intermediate protective layer further comprises an inner shielding layer, an outer shielding layer, a flame-retardant layer and an oxygen-barrier layer, and the insulating layers are arranged in two layers, namely a first insulating layer and a second insulating layer; the middle protective layer comprises from the inner layer to the outer layer: the inner shield layer, the first insulating layer, the outer shield layer, the second insulating layer, the filling layer, the belting layer, the flame retardant coating separates the oxygen layer, interior sheath, the armor.
10. The method for preparing the flame-retardant ceramifiable silicone rubber-sheathed cable according to claim 1, comprising the steps of:
respectively carrying out conductor monofilament drawing, monofilament annealing, conductor stranding, insulation extrusion, cabling and adding an intermediate protective layer; and finally, coating the flame-retardant ceramic silicon rubber sheath on the surface of the cable.
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| CN114709022B (en) | 2023-05-09 |
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