Man Made Mineral Fibers(MMMF)
Classification:
In contrast to naturally occurring mineral fibers, man made mineral fibers are amorphous; therefore, they are not crystals but glasses. Mineral elements are called fibers if the relation between the length and the diameter measures 3:1 or more. The oldest known (1300 years AC) MMMFs are found in Egyptian glass bottles. The technique to produce glass has been known since this time and since 1713 glass fibers have been used in textiles. The first mechanical way of producing slag fibers was announced in 1864, and a patent was given for the production of mineral wool in the USA in 1876. Fibers with a diameter smaller than 1 mm can be produced (flame-attenuated-production) since 1950. The first ceramic fibers were produced in France in 1967. The carcinogenic potency of the relatively young MMMFs is not exactly known because of the long latency period in the development of cancer. However, first reports suggest a higher risk of exposed persons, especially of those exposed to certain kinds of fibers (e.g. ceramic fibers, small diameter glass wool).
Synonyms/Trade Names:
Man Made Vitreous Fibers (MMVF), Refractory Fibers (ceramic fibers). A-S Carbon (graphite), Cem-Fiul (zirconia), Fiberfrax (carborundum), Franklin Fiber (gypsum), Fybex (potassium-octatitanate), Mackechnic (alumosilicate), Nicalon (ß-SiC), Polystal (GF), Refrasil C-1400 (silica fiber containing 3% chromium), Saffil (CF, aluminum oxide), Saffil alumina (alumina), Saffil Zirconia (zirconia), Triton (alumosilicate).
Chemistry/Composition:
The chemical composition is variable; a synopsis is given below (according to Waga 1990). In contrast to natural fibers, the chemical composition is artificially defined, and is associated with specific properties. Chemistry of MMMF in weight percent (according to Waga 1990, Büchner et al 1989, WHO/IARC 1988).
| |
SiO2 |
Al2O3 |
CaO |
MgO |
B2O |
Na2O |
K2O |
Fe2O3 |
| Glass wool | 50–65 | 3–15 | 5–15 | 2–5 | 1–2 | 1–18 | 1-18 | – |
| Textil Glass | | | | | | | | |
| Type A | 72.5 | 1.51) | 9 | 3.5 | – | 13 | – | – |
| Type C 2) | 65 | 4 1) | 14 | 3 | 5 | 0.5 | 8.0 | – |
| Type D | 74 | – | 0.5 | 0.2 | 22.5 | 1.3 | 1.5 | 0.2 |
| Type E 3) | 54.5 | 14.5 | 17 | 4.5 | 7.5 | 0.8 | 0.8 | 0.5 |
| Type R | 60 | 25 | 9 | 6 | – | 0.4 | 0.1 | 0.3 |
| Type S | 65 | 25 | – | 10 | – | – | – | trace |
| Type AR4) | 60.7 | – | – | – | – | 14.5 | 2.0 | trace |
| Cemfil5) | 71 | 1 | – | 11 | – | – | – | – |
| Type I | 54.5 | 14.5 | 22 | – | 8.5 | 0.5 | – | – |
| Type II | 65 | 4 | 14 | 3 | 5.5 | 8 | 0.5 | – |
| Type III | 59 | 4.5 | 16 | 5.5 | 3.5 | 11 | 0.5 | – |
| Type IV | 73 | 2 | 5.5 | 3.5 | – | 16 | – | – |
| Type V6) | 59.5 | 5 | – | – | 7 | 14.5 | – | – |
| Type VI7) | 34 | 3 | – | – | – | 0.5 | 3.5 | – |
| Slag fibers | | | | | | | | |
| German | 30–35 | 10–20 | 40–45 | 2-8 | – | – | - | - |
| American | 35–45 | 7–15 | 10–35 | 6–15 | – | – | - | - |
| Rock fibers | | | | | | | | |
| German | 50–55 | 6–15 | 25–35 | 2–6 | – | 2–3 | - | - |
| American | 34–44 | 10–20 | 25–41 | 1–8 | | – | – | - |
| Basaltic fbrs. | 45–50 | 12–15 | 9–12 | 7–10 | – | 2–4 | 10–12 | - |
| Ceramic fibers | 52.9 | 45.1 | – | – | 0.08 | <0.2 | – | <0.1 |
| Fiberfrax® | | | | | | | | |
| Bulk | 49.2 | 50.5 | – | – | – | 0.2 | 0.003 | 0.06 |
| Long sample8) | 44 | 51 | – | – | – | – | – | – |
| HSA9) | 43.4 | 53.9 | – | – | – | 0.1 | 0.1 | 0.8 |
| Fibermax® | | | | | | | | |
| Bulk | 72 | 27 | 0.05 | 0.05 | – | 0.1 | – | 0.02 |
| Alumina bulk | 95 5 | | – | – | – | – | – | – |
| Zirconia | | | | | | | | |
| Bulk 10) | – | <0.3 | – | – | – | – | – | – |
1) including Fe2O3
2) contains BaO: 10%
3) contains TiO2: 0.1% and F: 0.3%
4) contains ZrO2: 21.5%
5) contains ZrO2: 16% and Li2O: 1.0%
6) contains ZrO2: 4%; TiO2: 8% and F: 2%
7) contains PbO: 59%
8) contains ZrO2: 5%
9) contains TiO2: 1.6%
10) contains ZrO2: 92% and Y2O3: 8%
Optical fibers:
GeO2 or P2O5, containing quartz glass.
Ceramic fibers:
Wide range of composition (e.g. wollastonite).
Whiskers:
K2Ti6O13, CaSO4×1/2H2O, CaSO4, ß-SiC, -Si3N4, Al2O3 .
Structure:
Glass and mineral fibers:
All glasses are fast frozen meltings. The structure consists of small crystalline regions, i.e., of regularly spaced atoms. These are found in a network of randomly distributed atoms. Glasses are metastable. Carbon fibers: Carbon fibers are partially isotropic and have a small crystalline compartment. Anisotropic ones have intertwined graphite strands. In the HM type, the planes of the graphite fibrils are parallel to the fiber axis (graphite fibers). Opposite to the HT type, The HM type fibrils have a not exactly oriented graphite axis. Ceramic fibers display a glass structure with crystalline regions. Whiskers are small, defect-free, single crystals. The production process of glass fibers is as follows:
The raw production materials (E glass) are kaolin, quartz sand, colemanite (Ca(B3O4()6-5)×H2O), boric acid, limestone, dolomite, and fluorite. These are mixed, and melted at 1350° C for several days to clarify. Three different technical procedures are used to process the fibers:
a) The direct melting process:
the molten glass passes a cooling zone (1250° C) and is spun;
b) The marble melting process:
glass marbles are melted in spinning jets (only used for very fine fibers or special glass fibers);
c) The rod drawing process:
glass rods are fed into the melting zone and fibers are drawn onto a spool. Before being passed to the spinning machine, the fibers are cooled by dispersion of film-formers, adhesives, lubricants, antistatics, and various other materials (see below). The last spinned fragments are manufactured into end-products (e.g. cutting). Optical glass is produced by heating a quartz-filled form, which contains glass forming elements from gaseous compounds (e.g. GeCl4) (chemical vapor decomposition).
Production of mineral fibers:
The raw production materials are sand, limestone, dolomite, feldspar, kaolin, alumina-containing volcanic rocks, sodium carbonate, sodium sulfate, potassium carbonate, and boron minerals (glass wool); sedimentary or magmatic rocks (e.g clay, basalt, diabase) with small compartments of flux (e.g. dolomite) (rock wool); blast furnace slags (slag wool); pure ceramic raw material (e.g. kaolin, disthene) (ceramic fibers).
The raw materials are melted at 1200-1600° C, and processed in a) the centrifugal process: the melted glass is thrown out of holes located in the base of a rotating metalspinner; or
b) theCascade centrifugal process: the molten glass flows into one of three or four rotors, and is then transferred to the next rotor. Molten droplets flung from the rotor are twisted into fibers (diameter: 12-30 µm); or
c) the blowing process: the molten glass is drawn into fibers with a high speed gas jet (diameter: 3-12 µm); or
d) the drum centrifugal blowing process: the molten glass is thrown out of holes located in the base of a metal drum rotating at a high speed (diameter: 5-10 µm).
Normally, the fibers are lubricated with oil or binder (see below). Carbon fibers and carbon reinforced fibers are produced by thermal degradation (without oxygen) from nonmelting organic polymers (cellulose, cotton wool, sheep’s wool, polyacrylnitrile). Aluminum oxide fibers: The raw material is a fine particulate of aluminum oxide powder, which is spun and then dripped into ?-Al2O3 . Sometimes it is covered by SiO2 . Boron fibers are produced by chemical vapor decomposition. SiC fibers are produced by chemical vapor decomposition or by catalyst polymerization from polycarbosilanes (SiCl2(CH3)2); (diameter: 5-10 µm). Metal fibers are produced by a mechanical drawing process which includes: a) predrawn wires are pulled through orifices (steel fibers) (diameter: 150 µm); b) the bundle drawing process: the wires are embedded in a pipe mass (e.g. copper) (diameter 0.5 µm); c) the melt spinning process: molten metal is forced through dies as a thin jet into a liquid (diameter: 75 µm); d) the melt extraction process: cooled rotating discs pull fibers from a molten metal (diameter: 40 µm); e) the Taylor process: the molten metal is drawn through a metal-filled glass tube (diameter: 1 µm). Whiskers are K2Ti6O13 (diameter: 0.2-0.5 µm); CaSO4×1/2 H2O (diameter: 2 µm); CaSO4 (diameter: 2 µm); ß-SiC, ?-Si3N4, and Al2O3 (the diameters of the whiskers vary and cannot be exactly predetermined during the production process). The following binders are used in the production of MMMF: phenol formaldehyde resin, urea formaldehyde resin, melamine formaldehyde resin, polyvinyl acetate, vinsol resin, urea, silicones, dyes, ammonium sulfate, ammonium hydroxide, starch, carbon pigment, epoxy resins, pseudoepoxy resins, and bitumens.
Medical Importance:
Key Hazards:
Possibly fibrogenic and carcinogenic.
Involved Organs:
Lungs.
Exposure/Epidemiology:
MMMFs are used as a substitute for asbestos . Stone-, glass and slag wool are used in plastics (reinforcement, E glass), seals (reinforcement), frictional linings (reinforcement), cement (reinforcement), acoustic and thermic insulation, filters (AR glass) and air conditioning products. Endless glass fibers are used in electrical insulation. Specific stone and glass fibers are used in thermic insulation, airplanes and light transmission: SiC fibers and boron fibers in plastics (reinforcement) and aerospace industries; metal fibers as tire cord and in antistatic finishes; steel fibers in cement, aluminum silicate fibers for fire prevention, Al2O3 and Zr2O3 fibers in thermal insulation and hot gas filtration, tungsten fibers as incandescent filaments, carbon fibers for insulation, catalysts, plastics (reinforcement) and as woven textiles, whiskers as filling material, plastics (reinforcement), and in ceramics. In the past, natural and man made fibers were mixed sometimes to develop specific properties.
World production of various kinds of MMMF was estimated as follows:
| MMMF |
Production |
Year |
| Textile glass fibers | 1.35×106 tons | 1984 |
| Glass fiber | | |
| Reinforced plastics | 2×10 tons | 1986 |
| Mineral fiber | | |
| Insulating material | 8.8×106 tons | 1986 |
| Slag fibers | 70 000 tons | 1983 |
| Ceramic fibers | 72 000 tons | 1983 |
| Carbon | | |
| Reinforced fibers | 3000 tons | 1985 |
| Boron fibers | 40 tons | 1980 |
| Metal fibers | | |
| Steel fibers | 700 000 tons | 1986 |
| Whiskers | | |
| K2Ti6O13 | 600 tons | 1986 |
| CaSO4 1/2 H2O CaSO4 | 4000 tons/y | |
| ß-SiC, γ-Si3N4, Al2O34 | 100 tons/y | |
| All kinds | 6×106 tons | 1985 |
Thresholds:
Environmental concentrations range from 0.01-0.05 fibers/cm3 (glass insulation production); 0.032-0.72 fibers/cm3 (mineral wool facilities); 0.0082-7.6 fibers/cm3 (ceramic fibers); up to 50 fibers/cm3 (microfiber facilities). The Thresholds are as follows in various countries: Slo. Rep./Czec. Rep.: 8 mg/m3 (glass fiber); Denmark: 500 000 fibers/m3; Germany: 1 000 000 fibers/m3
(stationary old areas), 500 000 fibers/m3; Finland: 8h-exposure limit 10 mg/m3 (glass wool, mineral wool); France: 8h-exposure limit 10 mg/m3 (wool fibers); Great Britain: 200 000 fibers/m3; Netherlands: 500 000 fibers/m3 (stone and glass wool),
100 000 fibers/m3 (ceramic fibers); New Zealand: 100 000 fibers/m3 (<3 µm), Norway: 8h-exposure limit 5 mg/m3 (glass, rock, slag fibers); Poland: 200 000 fibers/m3 (length >5 µm); Russia: 8 mg/m3 (mineral fibers, glass fibers); Yugoslavia: 4 mg/m3 (mineral wool, glass wool, respirable dust); 12 mg/m3 (mineral wool, glass wool, total dust); Sweden: full working day 2 fibers/ml (glass fibers); USA: 300 000 fibers/m3 (length >10 µm).
Classification of MMMF in the German MAKlist: glass fibers “as though III A 2” (carcinogenic in animal experiments using intrapleural, intratracheal or intraperitoneal fiber applications); ceramic fibers “III A 2” (carcinogenic in animal inhalation experiments); slag wool “III B” (uncertain carcinogenic potency in animal experiments or insufficient data); stone wool “as though III A 2” (carcinogenic in animal experiments using intrapleural, intratracheal or intraperitoneal fiber applications).
Etiology/Pathophysiology:
In the lung, MMMFs break transversely and not parallel to their main axis. Asbestos fibers, especially amphibole asbestos fibers, break parallel to their main axis and become smaller in diameter, which is one reason for the deposit of these fibers in the terminal bronchioles. Thin (<0.25 µm) and long (>20 µm) asbestos fibers have the greatest carcinogenic potency.
Similar to asbestos fibers and depending on the length of the fibers, MMMFs can not be ingested completely by macrophages, and the lysosomal enzymes are released. The observed chromosomal changes of the macrophages depend on the length of the ingested fibers, and are suggested to be associated with the carcinogenic potency of the MMMFs. In the majority of cell transformation tests, only long (>10 µm) and thin (<1 µm) MMMFs displayed transformation activities.
Glass fibers were found to increase the expression of prostaglandins (membrane disturbance) and ß-glucuronidase (lysis of cells), depending on the applied dose. The expression of ornithin-decarboxylase was increased in hamster tracheal cells (glass wool). Chromosomal changes in hamster cells were increased, if exposed to thin and long fibers, independent of the composition of the applied fibers. Bioassay studies performed recently reported a weaker activity in glass fibers than chrysotile fibers; however, the observed activity was higher than that of crocidolite, amosite, or anthophyllite.
Animal studies often could not reveal a carcinogenic potency of inhaled MMMFs; however, intrapleural or intraperitoneal implantation of MMMFs in rats induced mesotheliomas (fibers <0.25 µm diameter and >8 µm length or <1.5 µm diameter and >4 µm length).
The migration rate of inhaled MMMFs into other organs was found to be less than that of asbestos fibers. Ceramic fibers (alumosilicates) and basaltic fibers displayed a high carcinogenic potency (as potent as some of the asbestos fibers) in animal experiments. A lipoproteinosis was noted by several authors. Whether the coating of the fibers influences the carcinogenic potency still remains an open question.
Only a small portion of the smallest MMMFs reach the alveoli and bronchioles in humans (see below). From there they are removed by the mucociliary clearing system and the macrophages, and pass the lymphatic vessels. MMMFs can be altered by phagocytosis of macrophages, physical forces (transverse breaks), or through chemical processes (corrosion), which alter especially the smallest glass and stone wool fibers (in vitro tests). Large fibers are coated with a proteinous gel on their surface.
Fibers exposed to alkaline solutions revealed corrosion (in vitro testing). The rate of corrosion was measured at 0.2-3.5 nm/d. The persistence of MMMFs in humans is estimated to be shorter than that of natural fibers. So called pseudo-asbestos bodies (ferruginous bodies) are often seen in MMMF-exposed workers. Smoking was found to be a co-carcinogenic factor; exposure to other toxic substances such as polycyclic aromatic hydrocarbons, arsenic (copper slag), chromium, formaldehyde, or silica may occur during the production process.
Diameter of MMMFs measured in slag, stone, and glass wool (according to Konietzko et al 1990):
| Diameter | Slag wool | Stone wool | Glass wool |
| ?m |
% |
% |
% |
| 0-3 | 60 | 36 | 26 |
| 3-6 | 26 | 42 | 23 |
| 6-9 | 6 | 13 | 15 |
| 9-12 | 5 | 5 | 15 |
| 12-15 | 2 | 3 | 11 |
| 15-18 | 1 | ! | 8 |
| >18 | 0 | 0 | 2 |
Lung Diseases:
MMMFs may induce mechanical irritation of the lung. MMMFs probably have a fibrogenic and cancerogenic potency similar to asbestos ; i.e., they can induce lung neoplasms and mesotheliomas.
Clinical Presentation:
Symptoms include chronic cough, shortness of breath on exercise, or those related to malignant growth.
Radiology:
Chest radiographs show foci of mucus retention, diffuse interstitial infiltrates, or circumscribed densities.
Lung Function:
Lung Function tests may be normal or display obstructive alterations.
Bronchoalveolar Lavage:
Rarely, the inhaled fibers can be detected in the lavage fluid.
Pathology:
Gross:
The lungs are of normal color and consistency, or reveal ectatic bronchi, irregular emphysema, or dense yellowish-white tumors.
Histology:
The alveoli can contain an increased number of macrophages, and collections of brown, often birefringent dust particles may be seen in the lymphatic tissue. The bronchial lumen can be ectatic and filled with greenish mucus, and mononuclear inflammatory infiltrates may be seen in the bronchial wall. The cell type of the associated malignancies does not differ from those seen in patients without exposure to MMMFs.
Prognosis:
Usually good; however, depending upon the underlying disease, and poor in cancer patients.
Additional Diseases:
Eyes:
Deposited particles induce mechanical irritation and consequent inflammation.
Upper Airways:
Relatively large particles (diameter >5 µm) are deposited on the exposed areas of the body during the production and handling of MMMFs and may induce a mechanical irritation (rhinitis, tracheitis, laryngitis). Asthmatic reactions can be seen.
Skin:
Mechanical irritation induces a mild erythema and seldom papulopustular lesions, interdigital maceration, and paronychia. Surface soils covering the fibers can induce allergies.
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search Pubmed for Man Made Mineral Fibe
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