JP2005336577A - Manganese phosphorous based chemical conversion treatment liquid and sealed type compressor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treatment liquid which stabilizes manganese phosphorous film grains into a uniform granular shape by adding cobalt to a manganese phosphate based chemical conversion treatment liquid, and to provide a sealed type compressor having high reliability and high performance by forming a uniform, granular manganese phosphorous film on the sliding part of a piston, a crankshaft or the like. <P>SOLUTION: A granular manganese phosphate film composed of crystal grains with a fine and round shape is formed on the surface of a piston, thus the surface roughness of the piston can be reduced, and leak can be reduced. In this way, the sealed type compressor of high performance having excellent wear resistance can be obtained. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a manganese phosphate chemical conversion treatment liquid for forming a manganese phosphate coating having excellent wear resistance and initial conformability on a sliding surface of a steel product such as a piston or a crankshaft, a refrigerator, an air The present invention relates to a hermetic compressor used for a condenser or the like.

  The conventional manganese phosphate treatment liquid has manganese ions of 0.10 to 1.00 mol / l, divalent iron ions of 0.50 mol, phosphate ions of 0.20 to 1.00 mol / l, and nitrate ions of 0.10. And a molar ratio of nitrate ion / phosphate ion is 0.5 to 1.5.

  In the manganese phosphate coating, iron on the sliding surface is etched into phosphoric acid, so that phosphoric acid is consumed, and manganese phosphate becomes insoluble tertiary phosphoric acid and free phosphoric acid. The acid grows to form a crystalline film (see, for example, Patent Document 1).

  Further, a manganese phosphate coating is formed on a sliding surface such as a piston or crankshaft of a hermetic compressor using a manganese phosphate chemical conversion treatment liquid (see, for example, Patent Document 2).

  Hereinafter, the conventional hermetic compressor will be described with reference to the drawings.

  FIG. 6 is a cross-sectional view of a conventional hermetic compressor described in Patent Document 2.

  In FIG. 6, an oil 2 and a reciprocating compression element 3 are accommodated in a sealed container 1, and a crankshaft 6 having a main shaft 4 and an eccentric shaft 5 as members constituting the compression element 3, and a crankshaft 6 are A cylinder block 8 that is rotatably supported and has a bore 7, a piston 9 that reciprocates in the bore 7, a connecting rod 10 that connects the eccentric shaft 5 and the piston 9, and a piston pin that connects the piston 9 and the connecting rod 10 11 is provided.

  Of the members constituting the compression element 3, the crankshaft 6 and the piston 9 which are sliding parts are both made of iron-based material, and a manganese phosphate film is formed on the surfaces of the crankshaft 6 and the piston 9. ing.

  The operation of the hermetic compressor configured as described above will be described below.

  When the crankshaft 6 is mechanically rotated while being supported by the cylinder block 8, the rotational force is transmitted to the piston 9 via the connecting rod 10 connected to the eccentric shaft 5. Is reciprocated to repeatedly compress and suck the refrigerant.

  In the reciprocating compression element 3, the main shaft 4 and the cylinder block 8 of the crankshaft 6, the eccentric shaft 5 of the crankshaft 6, the connecting rod 10, the connecting rod 10, the piston pin 11, and the like slide.

As the crankshaft 6 rotates, the oil 2 is supplied to each sliding portion described above, lubricates the sliding portion, and controls the seal between the piston 9 and the bore 7.
JP 2000-110719 A JP-A-7-90611

  However, in the above conventional configuration, when the manganese phosphate film is formed, the reaction of iron and phosphoric acid of the sliding member in the early stage of the chemical conversion treatment is slow, and the crystal of the film grows at a stretch in the latter half of the reaction. It has a problem that the surface roughness deteriorates.

  In addition, when a manganese phosphate coating is used for sliding parts such as the piston 9 and the crankshaft 6, the surface roughness deteriorates, so the contact surface pressure during sliding increases and wear increases. Had. Further, when used in the piston 9 or the cylinder block 8, there is a problem that the amount of leakage between the piston 9 and the bore 7 increases even if the clearance between the piston 9 and the bore 7 is set to be constant.

  The present invention solves the above-described conventional problems, and provides a treatment liquid that stabilizes manganese phosphate coating particles in a uniform granular shape by adding cobalt to the manganese phosphate-based chemical conversion treatment liquid. An object of the present invention is to provide a highly reliable and high performance hermetic compressor by forming a uniform granular manganese phosphate coating on a sliding portion such as a crankshaft.

  In order to solve the above-mentioned conventional problems, the manganese phosphate chemical conversion treatment liquid of the present invention is obtained by adding cobalt metal ions, and cobalt having a low ionization tendency is deposited on the steel surface. As a result, manganese phosphate It has the effect of promoting the initial reaction.

  Further, the hermetic compressor of the present invention is the one in which the sliding portion of the member constituting the compression element is subjected to manganese phosphate treatment with a manganese phosphate chemical conversion treatment solution to which cobalt metal ions are added. Can be made into a stable and uniform grain.

  Since the manganese phosphate chemical conversion treatment liquid of the present invention promotes the initial reaction of manganese phosphate, it is possible to form a stable and uniform granular manganese phosphate coating.

  In addition, the hermetic compressor of the present invention has a stable and uniform granular manganese phosphate coating formed on the sliding portion, thereby reducing the surface roughness of the sliding portion, providing high reliability and high refrigerating capacity. A high performance hermetic compressor can be provided.

  The invention described in claim 1 includes manganese ions of 0.10 to 1.00 mol / l, divalent iron ions of 0.10 to 0.50 mol / l, phosphate ions of 0.20 to 1.00 mol / l, and nitrate ions. Cobalt metal ions are added to an aqueous solution containing 0.10 to 1.00 mol / l, and the metal ions cobalt promote the initial reaction of the manganese phosphate treatment, so the crystal grains are finely granular. The manganese phosphate coating particles can be formed.

  The invention according to claim 2 is characterized in that the cobalt metal ion of the invention of claim 1 is 0.02 to 0.50 mol / l, and a more stable and uniform manganese phosphate coating is obtained. Therefore, it is possible to provide a manganese phosphate coating with higher performance and higher reliability.

  The invention according to claim 3 is obtained by subjecting at least one sliding portion of the member constituting the compression element to manganese phosphate chemical conversion treatment with the manganese phosphate chemical conversion treatment liquid according to claim 1 or 2, Since the shape of the crystal grains of the manganese phosphate coating is fine, the surface roughness of the sliding portion is reduced, and a hermetic compressor with excellent wear resistance can be provided.

  According to a fourth aspect of the present invention, in the invention of the third aspect, a reciprocating compression element is accommodated in a sealed container, and a crankshaft including a main shaft and an eccentric shaft as members constituting the compression element; A cylinder block that rotatably supports the crankshaft and forms a cylinder, a piston that reciprocates in the cylinder, a connecting rod that connects the eccentric shaft and the piston, and a manganese phosphate coating Since the shape of the crystal grains can be made stable and fine, the surface roughness is reduced, and a hermetic compressor with excellent wear resistance can be provided.

  Furthermore, when the manganese phosphate chemical conversion treatment is used for the piston or the cylinder block, the amount of leakage between the piston and the bore can be reduced, so that a hermetic compressor having a high refrigeration capacity can be provided.

  According to a fifth aspect of the present invention, in the third aspect of the invention, the rotary compression element is housed in a sealed container, the crankshaft as a member constituting the compression element, and the eccentric portion provided on the crankshaft. A roller piston that rolls along the inner wall surface of the cylinder fitted into the cylinder, a vane that is in contact with the outer peripheral surface of the roller piston and partitions the cylinder inner space into a high-pressure chamber and a low-pressure chamber, and the crankshaft is pivotally supported. And a pair of bearing plates that close both end faces of the cylinder, and the shape of the crystal grains of the manganese phosphate film can be stably made finer, the surface roughness becomes smaller, and when sliding Therefore, it is possible to provide a highly reliable hermetic compressor.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 1 is a characteristic diagram showing the growth of the chemical conversion film with respect to the chemical conversion treatment time.

  Hereinafter, an embodiment of the present invention will be described with reference to FIG.

  In FIG. 1, manganese ions 0.10 to 1.00 mol / l, divalent iron ions 0.10 to 0.50 mol / l, phosphate ions 0.20 to 1.00 mol / l, nitrate ions 0.10 to 1 When an aqueous solution containing 0.000 mol / l is subjected to a chemical conversion treatment with a manganese phosphate-based chemical conversion solution in which cobalt metal ions are added at 0.25 mol / l, 0.50 mol / l, and 0.70 mol / l, respectively, The characteristic comparison at the time of performing a chemical conversion treatment with the conventional manganese phosphate chemical conversion treatment liquid to which no metal ion is added is shown.

  The characteristics are compared with the growth of the chemical conversion film with respect to the chemical conversion treatment time. The growth of the chemical conversion film is performed by masking a part of the piston, and after performing chemical conversion treatment with a manganese phosphate chemical conversion treatment liquid, using a shape measuring device. The film thickness obtained from the level difference between the non-processed part and the processed part is obtained by measuring with time.

  Also, it is iron-based materials that are subjected to chemical conversion treatment.

  As shown in FIG. 1, the chemical conversion treatment with the conventional manganese phosphate chemical conversion solution does not generate a film in the initial reaction until 1 minute after the start of the reaction, and reacts all at once in the latter half of the reaction.

  On the other hand, a film formed by chemical conversion treatment with a manganese phosphate chemical conversion solution to which cobalt metal ions are added at 0.25 mol / l, 0.50 mol / l, and 0.70 mol / l, respectively, produces a film in the initial reaction.

  Furthermore, Table 1 shows the surface state of the iron-based material after the chemical conversion treatment.

  As shown in Table 1, the film subjected to the chemical conversion treatment with the conventional manganese phosphate chemical conversion solution has a surface roughness Ra of more than 0.40 μm, and the observation result with SEM shows that the particles are needle-like. On the other hand, the film subjected to the chemical conversion treatment with the manganese phosphate chemical conversion treatment solution to which cobalt metal ions are added has a surface roughness Ra of 0.20 μm or less, and the SEM observation results show that the particles are finely granular.

  This is because the amount of cobalt metal ions added to the manganese phosphate chemical conversion treatment solution means that cobalt is present in the manganese phosphate chemical conversion treatment solution, and the ionization tendency is small on the surface of the iron material. This is because cobalt is precipitated and promotes the reaction of manganese phosphate.

  Moreover, even if it adds cobalt exceeding 0.50 mol / l, although the effect commensurate with addition is not acquired, cost will become high, Therefore It can be said that the addition amount of cobalt exceeding 0.50 mol / l is useless.

  Therefore, by adding cobalt metal ions to the manganese phosphate chemical conversion treatment liquid, the manganese phosphate coating particles can be made finer and the effect of reducing the surface roughness can be obtained.

  In addition, nitrite, nitrate, chlorate, bromate and other accelerators are generally used in chemical conversion treatment, but even if these accelerators are used in addition, the effect of depositing cobalt on the iron surface In addition, since the surface roughness is further reduced, it is more effective to use an accelerator such as nitrous acid, nitrate, chlorate and bromate together.

(Embodiment 2)
FIG. 2 is a cross-sectional view of a reciprocating hermetic compressor according to the second embodiment of the present invention, and FIG.

  Hereinafter, embodiments of the present invention will be described with reference to FIGS. In addition, detailed description is abbreviate | omitted about the manganese phosphate type | system | group chemical conversion treatment liquid demonstrated in Embodiment 1. FIG.

  In FIG. 2, an oil 102 and a reciprocating compression element 103 are accommodated in a sealed container 101, and a crankshaft 106 having a main shaft 104 and an eccentric shaft 105 as members constituting the compression element 103, and a crankshaft 106 are A cylinder block 108 that is rotatably supported and has a bore 107, a piston 109 that reciprocates in the bore 107, a connecting rod 110 that connects the eccentric shaft 105 and the piston 109, and a piston pin that connects the piston 109 and the connecting rod 110. 111 is provided.

  Of the members constituting the compression element 103, the piston 109 and the crankshaft 106, which are sliding parts, are made of iron-based materials. By the process described in the first embodiment, the piston 109 and the crankshaft 106 are A manganese phosphate film is formed on the surface.

  The operation and action of the reciprocating hermetic compressor configured as described above will be described below.

  When the crankshaft 106 is mechanically rotated while being supported by the cylinder block 108, this rotational force is transmitted to the piston 109 via the connecting rod 110 connected to the eccentric shaft 105, and the piston 109 is moved into the bore 107. Is reciprocated to repeatedly compress and suck the refrigerant.

  At this time, a manganese phosphate film is formed on the surface of the piston 109 so that the inside of the bore 107 can be smoothly reciprocated. This manganese phosphate coating uses the manganese phosphate chemical conversion treatment solution to which the cobalt metal ion described in the first embodiment is added. As described in detail in the first embodiment, the manganese phosphate coating is used. The coating particles can be finely divided into round particles, and the effect of reducing the surface roughness can be obtained.

  Therefore, since the surface roughness can be reduced by forming the manganese phosphate film on the surface of the piston 109 that slides in the bore 107, the sliding surface pressure of the sliding portion can be reduced, and the sliding portion Abrasion resistance is improved.

  Further, a manganese phosphate film is formed on the surface of the crankshaft 106 that is mechanically rotated while being supported by the cylinder block 108. This manganese phosphate coating is also made using a manganese phosphate chemical conversion treatment solution to which cobalt metal ions are added, and the effect of reducing the surface roughness by making the manganese phosphate coating particles finer and round. Is obtained.

  Therefore, since the surface roughness can be reduced by forming the manganese phosphate film on the surface of the crankshaft 106, the sliding surface pressure of the sliding part can be reduced, and the wear resistance of the sliding part is improved. To do.

  Next, the sealing characteristics of the sliding part will be described.

  As the crankshaft 106 rotates, the oil 102 is supplied to each sliding portion, lubricates the sliding portion, and controls the seal between the piston 109 and the bore 107.

  Here, as described in the first embodiment, the piston 109 in which the manganese phosphate film is added using the manganese phosphate-based chemical conversion treatment solution to which cobalt metal ions are added, and the conventional method in which cobalt metal ions are not added. The result of having compared the characteristic using the piston 9 which produced | generated the manganese phosphate membrane | film | coat using the manganese phosphate type | system | group chemical conversion treatment liquid is demonstrated.

  In FIG. 3, the clearance in the radial direction between the piston 109 and the bore 107 is the same as that of a conventional reciprocating hermetic compressor, the refrigerant and oil 102 used are the same for R134a and ester oil (VG10), and the operating frequency is the same. The characteristic difference of the refrigerating capacity when operating at 27 Hz is shown.

  As shown in FIG. 3, the manganese phosphate film to which cobalt metal ions are added has a smaller amount of leakage between the piston 109 and the bore 107 than the conventional manganese phosphate film. It is high.

  This is because the addition of cobalt metal ions promotes the initial reaction during the chemical conversion treatment of manganese phosphate, and the surface roughness is reduced, so that the sealing performance between the piston 109 and the bore 107 is improved. Because.

  Therefore, the amount of leakage between the piston 109 and the bore 107 can be reduced by making the crystal grains of the manganese phosphate film in the sliding portion fine and stable over the entire surface, thereby reducing the amount of leakage between the piston 109 and the bore 107. The effect of improving ability can be obtained.

  In the present embodiment, the results are obtained at the time of operation at an operating frequency of 27 Hz. However, even if the operating frequency is other than 27 Hz, the effect of improving the sealing performance of the piston 109 and the bore 107 can be obtained similarly. Needless to say, the effect of improving the refrigerating capacity can be obtained similarly.

  Further, in this embodiment, the chemical conversion treatment was performed on the piston 109, and the description was made with the combination of R134a and ester oil. Since the improvement effect is obtained in the same manner, it goes without saying that the improvement effect of the refrigerating capacity is obtained similarly.

  In particular, the same effect can be obtained by combining R600a and R290, which have a large amount of refrigerant dissolved in the oil and lower the viscosity of the oil, and increase the amount of leak, with mineral oil and oils such as alkylbenzene, ester, polyvinyl ether, and polyalkylene glycol. Is obtained.

  Further, in the present embodiment, the explanation is given for the chemical conversion treatment of the piston 109. However, even if the chemical conversion treatment is performed on the sliding portion of the cylinder block 108, the effect of improving the sealing performance between the piston 109 and the bore 107 is obtained in the same manner. Therefore, it goes without saying that the effect of improving the refrigerating capacity can be obtained similarly.

(Embodiment 3)
FIG. 4 is a sectional view of a rotary hermetic compressor according to the third embodiment of the present invention, and FIG. 5 is a characteristic diagram showing the amount of wear in the same embodiment.

  Hereinafter, an embodiment of the present invention will be described with reference to FIGS. In addition, detailed description is abbreviate | omitted about the manganese phosphate type | system | group chemical conversion treatment liquid demonstrated in Embodiment 1. FIG.

  In FIG. 4, a rotary compression element 202 is accommodated in an airtight container 201, and is fitted to a crankshaft 203 as a member constituting the compression element 202 and an eccentric portion 209 provided on the crankshaft 203. A roller piston 205 that rolls along the inner wall surface, a vane 206 that contacts the outer peripheral surface of the roller piston 205 and partitions the inner space of the cylinder block 204 into a high-pressure chamber and a low-pressure chamber, and supports the crankshaft 203 and the cylinder block A pair of bearing plates 207 and 208 for closing both end faces of 204 are provided.

  Of the members constituting the compression element 202, both the crankshaft 203 and the roller piston 205, which are sliding parts, are made of iron-based materials, and the manganese phosphate coating is formed by the process described in the first embodiment. Is formed on the surface.

  The operation and action of the rotary hermetic compressor configured as described above will be described below.

  When the crankshaft 203 mechanically rotates, this movement is transmitted to the roller piston 205 fitted to the eccentric portion 209 and rotates while sliding along the inner wall surface of the cylinder block 204. Since the roller piston 205 and the vane 206 divide the space in the cylinder block 204 into a high pressure chamber and a low pressure chamber, the gas absorbed in the low pressure chamber is compressed by the rotation of the roller piston 205 and transferred to the high pressure chamber. Repeat exercise.

  At this time, since the manganese phosphate coating is formed on the surfaces of the crankshaft 203 and the roller piston 205, sliding during the rotational motion can be performed smoothly. In addition, since the crystal grain shape is fine and round, a granular manganese phosphate coating is formed, the surface roughness is small, and as a result, the sliding surface pressure of the sliding part can be reduced and the wear resistance is improved. .

  The experimental results regarding the wear resistance are shown in FIG. FIG. 5 shows a sample in which a manganese phosphate film is formed using a chemical conversion treatment liquid in which cobalt metal ions are added to an FC200 disk and a conventional chemical conversion treatment liquid in which cobalt metal ions are not added. It is a ring on disk test result which implemented the test for 5 minutes by the load of 100N using the sample which produced | generated the membrane | film | coat. The refrigerant is R407C, and ester oil (VG15) is used.

  As can be seen from FIG. 5, the wear of 2 μm was observed for the conventional manganese phosphate coating, whereas the wear of the manganese phosphate coating to which cobalt metal ions were added was 0.5 μm. This is because, in the conventional manganese phosphate coating, the crystal shape grows in a needle shape and the surface roughness is increased, whereas in the manganese phosphate coating to which cobalt metal ions are added, the crystal shape is granular. This is because the surface roughness is small and the contact surface pressure during sliding is reduced, thereby improving the wear resistance.

  Therefore, by making the crystal grains of the manganese phosphate coating on the sliding part fine and stable over the entire surface, the contact surface pressure of the sliding part can be reduced, and a highly reliable seal with excellent wear resistance. A mold compressor can be provided.

  In the present embodiment, the roller piston 205 and the crankshaft 203, which are sliding parts of the rotary hermetic compressor, have been described by coating the surface with fine granular manganese phosphate particles. Applicable to sliding parts of closed type compressors, sliding parts such as crankshafts, cylinder blocks, pistons and piston pins of reciprocating hermetic compressors, and sliding parts of scroll type hermetic compressors However, by making the crystal grains of the manganese phosphate coating on the sliding part fine and stable over the entire surface, the effect of reducing the contact surface pressure of the sliding part can be obtained in the same way, and the wear resistance And a highly reliable hermetic compressor with excellent reliability.

  As described above, the manganese phosphate-based chemical conversion treatment liquid and the hermetic compressor according to the present invention can form the crystal grains of the manganese phosphate film into stable particles, and can suppress the surface roughness to a small level. Therefore, it can be applied to various sliding materials.

The characteristic view which showed the growth of the chemical conversion film with respect to the chemical conversion treatment time in Embodiment 1 of this invention Sectional drawing of the reciprocating hermetic type compressor in Embodiment 2 of this invention Characteristics of leak amount and refrigeration capacity in the same embodiment Sectional drawing of the rotary hermetic compressor in Embodiment 3 of this invention Characteristic diagram showing the amount of wear in the same embodiment Cross section of a conventional hermetic compressor

Explanation of symbols

101, 201 Sealed container 103, 202 Compression element 104 Main shaft 105 Eccentric shaft 106, 203 Crankshaft 108 Cylinder block 109 Piston 110 Connecting rod 204 Cylinder 205 Roller piston 206 Vane 207, 208 Bearing plate 209 Eccentric part

Claims (5)

  Manganese ions 0.10 to 1.00 mol / l, divalent iron ions 0.10 to 0.50 mol / l, phosphate ions 0.20 to 1.00 mol / l, nitrate ions 0.10 to 1.00 mol / l A manganese phosphate-based chemical conversion treatment solution in which cobalt metal ions are added to an aqueous solution containing.   The manganese phosphate chemical conversion treatment liquid according to claim 1, wherein the metal ion of cobalt is 0.02 to 0.50 mol / l.   A hermetic compressor in which at least one sliding portion of a member constituting the compression element is subjected to manganese phosphate chemical conversion treatment with the manganese phosphate chemical conversion treatment solution according to claim 1 or 2.   A reciprocating compression element is housed in an airtight container, a crankshaft having a main shaft and an eccentric shaft as members constituting the compression element, and a cylinder block that rotatably supports the crankshaft and forms a cylinder The hermetic compressor according to claim 3, further comprising: a piston that reciprocates in the cylinder; and a connecting rod that connects the eccentric shaft and the piston.   A roller that accommodates a rotary compression element in a sealed container and rolls along a crankshaft as a member constituting the compression element and an inner wall surface of a cylinder fitted to an eccentric portion provided on the crankshaft A piston, a vane that is in contact with the outer peripheral surface of the roller piston and partitions the inner space of the cylinder into a high pressure chamber and a low pressure chamber, and a pair of bearing plates that pivotally support the crankshaft and close both end surfaces of the cylinder. The hermetic compressor according to claim 3 provided.