BACKGROUND OF THE INVENTIONThis invention relates generally to nonwoven fibers made from a thermoplastic resin.[0001]
Thermoplastic resins have been extruded to form fibers, fabrics and webs for a number of years. Common thermoplastics for this application are polyolefins, particularly polyethylene and polypropylene. Other materials such as polyesters, polyetheresters, polyamides and polyurethanes are also used to form nonwoven fabrics.[0002]
Nonwoven fabrics or webs are useful for a wide variety of applications such as personal care products, towels, recreational or protective fabrics and as geotextiles and filter media. The nonwoven fibers used in these applications may be made by many processes known in art, such as spunbonding and meltblowing. Nonwoven fibers may be processed into webs through bonding and carding processes, airforming (airlaying), and other processes.[0003]
Fibers are commonly consolidated to form a web by adhesive bonding, mechanical bonding such as hydroentangling and by ultrasonic and thermal bonding processes using bonding fibers. These processes work well but have individual idiosyncratic drawbacks. Adhesive bonding and hydroentangling, for example, often necessitate the removal of water, a process involving the addition of more energy for a rather lengthy time. Ultrasonic bonding is also an energy intensive activity involving energy being added somewhat randomly to a web. Thermal bonding also involves the addition of energy to the web in a relatively slow process to melt particular binder fibers.[0004]
A process wherein the binder fibers could be heated more rapidly to their melting temperature would be very advantageous for high-speed industrial applications. An improved binder fiber that could reach its melting temperature under the proper conditions in a matter of fractions of a second would significantly reduce processing and production time and thus increase manufacturing efficiency and reduce product cost. Such binder fibers would probably also use less energy than fibers that more slowly reached their melting temperature since less energy would probably be absorbed by adjacent materials. It is an object of this invention to produce such a fiber.[0005]
SUMMARY OF THE INVENTIONThe objects of this invention are achieved by a fiber having an energy receptive additive capable of dielectric heating and having a dielectric loss (as defined below) of between 0.5 to 15. The fiber more particularly should have a dielectric loss of at least 1 and still more particularly have a dielectric loss of at least 5. It is preferred that the fiber have a dielectric loss tangent (as defined below) of between 0.1 to 1, more particularly between 0.3 to 0.7.[0006]
The fiber may be made from a synthetic polymer selected from groups such as polyolefins, polycaprolactones, polyamides, polyetheramides, polyurethanes, polyesters, Poly (meth) acrylates metal salts, polyether, poly(ethylene-vinyl acetate) random and block copolymers, polyethylene-b-polyethylene glycol block copolymers, polypropylene oxide-b-polyethylene oxide copolymers and blends thereof.[0007]
The energy receptive additive may be, for example, carbon black, magnetite, silicon carbide, calcium chloride, zircon, ferrite, tin oxide, silicon carbide, calcium chloride, alumina, magnesium oxide, and titanium dioxide. The energy receptive additive may be present in an amount between 2 and 40 weight percent, more particularly between 5 and 15 weight percent, of the total fiber weight.[0008]
The fiber may also be a bicomponent fiber of the sheath/core or island in the sea type. The energy receptive additive may be present in the sheath or core of a sheath/core type bicomponent fiber.[0009]
The fiber may also a biconstituent fiber. The fiber may be crimped, extendible and/or elastic and the energy receptive additive may be carbon black in an amount between 2 and 40 weight percent.[0010]
A particular embodiment is a fiber having an energy receptive additive in an amount between 5 and 15 weight percent, synthetic polymer and having a dielectric loss of at least 0.5.[0011]
Nonwoven webs may be produced with the fibers of this invention as well.[0012]
DEFINITIONSAs used herein the term “nonwoven fabric or web” means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric. Nonwoven fabrics or webs have been formed from many processes such as for example, meltblowing processes, spunbonding processes, and bonded carded web processes. The basis weight of nonwoven fabrics is usually expressed in ounces of material per square yard (osy) or grams per square meter (gsm) and the fiber diameters useful are usually expressed in microns. (Note that to convert from osy to gsm, multiply osy by 33.91).[0013]
As used herein the term “meltblown fibers” means fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity, usually hot, gas (e.g. air) streams which attenuate the filaments of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241 to Butin et al. Meltblown fibers are microfibers which may be continuous or discontinuous, are generally smaller than 10 microns in average diameter, and are generally tacky when deposited onto a collecting surface.[0014]
“Spunbonded fibers” refers to small diameter fibers that are formed by extruding molten thermoplastic material as filaments from a plurality of fine capillaries of a spinneret. Such a process is disclosed in, for example, U.S. Pat. No. 4,340,563 to Appel et al. and U.S. Pat. No. 3,802,817 to Matsuki et al. The fibers may also have shapes such as those described, for example, in U.S. Pat. No. 5,277,976 to Hogle et al. which describes fibers with unconventional shapes.[0015]
As used herein the term “bicomponent fibers” refers to fibers which have been formed from at least two polymers extruded from separate extruders but spun together to form one fiber. Bicomponent fibers are also sometimes referred to as multicomponent or conjugate fibers. The polymers are usually different from each other though bicomponent fibers may be monocomponent fibers. The polymers are arranged in substantially constantly positioned distinct zones across the cross-section of the bicomponent fibers and extend continuously along the length of the bicomponent fibers. The configuration of such a bicomponent fiber may be, for example, a sheath/core arrangement wherein one polymer is surrounded by another or may be a side by side arrangement, a pie arrangement or an “islands-in-the-sea” arrangement. Bicomponent fibers are taught in U.S. Pat. No. 5,108,820 to Kaneko et al., U.S. Pat. No. 4,795,668 to Krueger et al., U.S. Pat. No. 5,540,992 to Marcher et al. and U.S. Pat. No. 5,336,552 to Strack et al. Bicomponent fibers are also taught in U.S. Pat. No. 5,382,400 to Pike et al. and may be used to produce crimp in the fibers by using the differential rates of expansion and contraction of the two (or more) polymers. For two component fibers, the polymers may be present in ratios of 75/25, 50/50, 25/75 or any other desired ratios. The fibers may also have shapes such as those described in U.S. Pat. Nos. 5,277,976 to Hogle et al., 5,466,410 to Hills and 5,069,970 and 5,057,368 to Largman et al., which describe fibers with unconventional shapes.[0016]
As used herein the term “biconstituent fibers” refers to fibers which have been formed from at least two polymers extruded from the same extruder as a blend. The term “blend” is defined below. Biconstituent fibers do not have the various polymer components arranged in relatively constantly positioned distinct zones across the cross-sectional area of the fiber and the various polymers are usually not continuous along the entire length of the fiber, instead usually forming fibrils or protofibrils which start and end at random. Biconstituent fibers are sometimes also referred to as multiconstituent fibers. Fibers of this general type are discussed in, for example, U.S. Pat. Nos. 5,108,827 and 5,294,482 to Gessner. Bicomponent and biconstituent fibers are also discussed in the textbook[0017]Polymer Blends and Compositesby John A. Manson and Leslie H. Sperling, copyright 1976 by Plenum Press, a division of Plenum Publishing Corporation of New York, IBSN 0-306-30831-2, at pages 273 through 277.
As used herein the term “blend” means a mixture of two or more polymers while the term “alloy” means a sub-class of blends wherein the components are immiscible but have been compatibilized. “Miscibility” and “immiscibility” are defined as blends having negative and positive values, respectively, for the free energy of mixing. Further, “compatibilization” is defined as the process of modifying the interfacial properties of an immiscible polymer blend in order to make an alloy.[0018]
“Bonded carded web” refers to webs that are made from staple fibers which are sent through a combing or carding unit, which separates or breaks apart and aligns the staple fibers in the machine direction to form a generally machine direction-oriented fibrous nonwoven web. This material may be bonded together by methods that include point bonding, through air bonding, ultrasonic bonding, adhesive bonding, etc.[0019]
“Airlaying” is a well-known airforming process by which a fibrous nonwoven layer can be formed. In the airlaying process, bundles of small fibers having typical lengths ranging from about 3 to about 52 millimeters (mm) are separated and entrained in an air supply and then deposited onto a forming screen, usually with the assistance of a vacuum supply. The randomly deposited fibers then are bonded to one another using, for example, hot air or a spray adhesive. The production of airlaid nonwoven composites is well defined in the literature and documented in the art. Examples include the DanWeb process as described in U.S. Pat. No. 4,640,810 Laursen et al. and assigned to Scan Web of North America Inc, the Kroyer process as described in U.S. Pat. No. 4,494,278 Kroyer et al. and U.S. Pat. No. 5,527,171 Soerensen assigned to Niro Separation a/s, the method of U.S. Pat. No. 4,375,448 Appel et al assigned to Kimberly-Clark Corporation, or other similar methods.[0020]
“Personal care product” means products for the absorption of body exudates, such as diapers, training pants, disposable swim wear, absorbent underpants, adult incontinence products, bandages, veterinary and mortuary products, and feminine hygiene products like sanitary napkins and pantiliners.[0021]
TEST METHODSDielectric constant and dielectric loss: The following equations are based on measurements of the dielectric constant (ε′) and dielectric loss (ε″) from a solid or liquid sample using a technique requiring a Network analyzer combined with a Coaxial probe [1-7]. Unless otherwise explicitly stated the equations herein apply to equivalent volumes of material unless specific volume terms are incorporated. Generally, temperature changes relative to heating rates are derived in terms of degrees Celsius per second.[0022]
Films and solid blocks may be measured as received, while powdered and pelleted samples should be converted to films or solid blocks for measurements, or may be evaluated using a Cavity Perturbation Method. Dielectric property values of powdered samples measured using a coaxial probe method must be corrected using a volume fraction conversion.[0023]
For comparative measurements, all powders and pellets are converted to films and solids to avoid the requirement of the volume fraction conversion. The reason for this is that powdered and rough samples create micro-air-gaps between the material under test (MUT) and the probe or electrode surface. This inherent air gap causes a decrease in capacitance, resulting in a decrease in the measured capacitance and a corresponding decrease in the resulting dielectric loss values. Rough surfaces can cause a decrease in values of from 5-20 percent, while powdered samples can result in decreases of up to 100 percent.[0024]
General computational formulas have been derived from the literature for computations relating dielectric constant and dielectric loss measurements to a set of heating rate equations. These relationships can also allow general understanding of the interrelational effects of the Applied Electric Field (E), and Power (P) of a microwave source; density and specific heats of the MUT; and the estimated relative heating rates of a target material. The algebraic relationships are described here in general form and for specific cases. All variables and terms in their respective units are defined in a single section following the equations.[0025]
Computational Formulas[0026]
The penetration depth (in centimeters) of an applied field of microwave energy is defined by the depth of the MUT where ˜63.2 percent of the energy has been dissipated. This relationship in depth units equivalent to units used for λ
[0027]0is given in general form as
And the Half-Power Penetration Depth (in λ
[0028]0equivalent units) representing the depth of the MUT where ˜50.0 percent of the energy has been dissipated is calculated using the relationship in Equation (2).
Note 1: A dimension similar to the D
[0029]50is the Radio Absorption Length which is defined as
Note 2: (a) A Relative Heating Rate has been determined for organic liquids under specific measurement conditions. The relative heating rate as a dimensionless number is given as
[0030](b) Additionally, an estimated heating rate for organic liquids in ° C.sec
[0031]−1under specific conditions (200 mL water, 25 mL MUT, and 630 w) is estimated by
The Relative Absorbed Power per unit volume is given as[0032]
Pv=kpνE2ε″ (3)
In general, the Heating Rate Equation in ° C. per second for an MUT is described by
[0033]A series of calculations is made, using the measured dielectric properties of a material, to estimate the relative heating rate (in ° C. per second) of a material. A simplified computational formula used is
[0034]Note 3: A power loss (as heat) is affected by the principles of convection, radiation, and conduction as energy losses, or by direct absorption by liquids or high loss materials (e.g., water). The absorbed power (in watts) is given by the general relationship P[0035]A=P0−PLwhere PAis the power absorbed (in watts), P0is the available power as initial power (in watts), and PLis the power lost as heat (as ΔT).
Note 4: The target sample load size follows a direct relationship with the heating time and the heating rate, that is, twice the material requires twice the energy input to maintain an equivalent heating rate.[0036]
The basic microwave heating equation is as[0037]
P0=2πνε0ε′tanδE2=2πνε0ε″Ei2 (6)
The computational form of Equation (6), with ν in GHz and E in volts-cm[0038]−1, is presented as
P0i=5.56×1031 4·ν·ε″·E2 (7)
So applying Equation (7) for free water at 20° C. (ε″=12.48) and for an applied microwave field at ν=2.45 GHz we have[0039]
P0i≈1.70×10−2·E2 (8)
And combining Equation (5) with Equation (8) we obtain[0040]
ΔT=4.0×10−3·t·E2 (9)
Note 5: Solving Equation (9) for one ° C. per second yields an E of 15.81 volts·cm[0041]−1.
The general case for microwave heating rate is expressed as
[0042]Noting that the expression[0043]
2πε0itν (11)
has a value of 1.3622×10
[0044]−3for 2450 MHz, and 5.0874×10
−4for 915 MHz, it follows from Equations (5) and (10) that the rate of change in temperature is given by
Solving Equation (12) for E we obtain
[0045]An additional computational form for calculating an increase in temperature relative to a material, given a specific microwave field strength (E) with ν in units of Hz, is given by
[0046]The estimated Electric Field Strength (E) given an amount of Power available for conversion to heat is given as
[0047]Note 6: By the relationships described in Fresnel reflection we know R[0048]∥+T∥=1 and R⊥+T⊥=1.
The Loss Tangent can be used to calculate the relative Electrical Conductivity of a material under test (χ
[0049]e) and its Resistivity (ρ
e) using
And solving for (χ
[0050]e) from Equation (16) gives
Note 7: Using Equation (17) the relative Resistivity (ρ
[0051]e) is calculated as
Symbols and Abbreviations[0052]
c is the speed of light (as 2.9979×10[0053]10cm·sec.−1)
C[0054]pis the specific heat of the target material (in cal.·g−1)
d is the density of the target material (in g·cm[0055]−3)
D is the power dissipation factor[0056]
D[0057]50is the Half-Power Penetration Depth (in cm) representing the depth of material where 50 percent of the initial power is dissipated
D[0058]pis the 63 percent-Power Penetration Depth (in cm) representing the depth of material where 63.2 percent of the initial power is dissipated
χ[0059]eis the relative Electrical Conductivity of an MUT
E is the rms value of the applied electric field (in volts·cm[0060]−1)
E[0061]iis the rms value of the applied electric field (in volts·m−1)
ε′ is designated here as the measured dielectric constant of a material (a.k.a. κ)[0062]
ε″ is designated here as the measured dielectric loss of a material[0063]
ε[0064]0is the dielectric permittivity of free space (as 8.86×10−12farad·m−1)
ε[0065]0iis the adjusted dielectric permittivity constant (as 8.86×10−5farad·cm−1)
ε[0066]ris the complex relative permittivity
j is a proportionality constant[0067]
k is a unit conversion proportionality constant equal to 1.333×10[0068]−7
k[0069]eis an efficiency term constant as a fraction of 1, where 1 represents 100 percent efficiency
k[0070]his a proportionality constant for unit conversion equal to 4.186 for GHz and 4186 for MHz
k[0071]pis a proportionality constant for unit conversion equal to 5.561×10−7
I[0072]Ris the Radio Absorption Length (depth of penetration in units of the λ0term)
λ[0073]0is the wavelength (in cm) of the incident microwave energy converted using λ0=c (in cm·sec.−1)×ν−1(in Hz). Note: 2450 MHz=12.24 cm, and 915 MHz=32.76 cm
MUT is a Material Under Test[0074]
ν (nu) is the frequency of the applied microwave field (in MHz)[0075]
P[0076]0is the applied initial Power (in watts·m31 3); Note: 1 watt=14.33 g·calories·min−1
P[0077]0iis a computational form of the applied initial Power (in watts·cm−3)
P[0078]Ais the Power absorbed (in watts per unit volume)
P[0079]Lis the Power lost as thermal loss (in watts per unit volume)
P[0080]ν is the Relative Absorbed Power (as applied for a specified volume, in watts per unit volume)
Q is the power quality factor[0081]
R[0082]195 represents the reflected power or energy for incident energy perpendicular in orientation relative to the electronic surface vector of the MUT
R[0083]∥ represents the reflected power or energy for incident energy parallel in orientation relative to the electronic surface vector of the MUT
ρ[0084]eis the relative Resistivity of the MUT
t is the time duration of an applied field (in seconds)[0085]
T[0086]⊥ represents the transmitted power or energy for incident energy perpendicular in orientation relative to the electronic surface vector of the MUT
T[0087]∥ represents the transmitted power or energy for incident energy parallel in orientation relative to the electronic surface vector of the MUT tanδ is the ratio of ε″/ε′, and so ε′·tanδ=ε″
ΔT is a unit temperature change in the target (in ° C.·sec.[0088]−1)
W is the weight of the sample target (in grams)[0089]
Sample Calculation[0090]
It is desired to measure the broad-band dielectric relaxation spectrum for a series of specially created polymers and polymer mixtures and report dielectric properties for the commercially available microwave frequencies of 915 MHz and 2450 MHz. All samples were evaluated at 25° C. All samples as pellets or fibers were converted to polymer films of approximately 1 mm thickness before measurements. Dielectric data were archived for the full range of 300 kHz to 3.0 GHz. Sample Numbers and designations for the special mixtures studied were as shown in Table 1.[0091]
The measurements are made using a Network Analyzer with a low power external electric field (i.e., 0 dBm to +5 dBm) typically over a frequency range of 300 kHz to 3 GHz, although Network Analyzers to 20 GHz are readily available, for example, the HP 8720D Dielectric Probe available from the Hewlett-Packard Company (HP). Samples are measured by placing them in contact with a coaxial reflectance probe yielding low-loss measurements for liquids, semi-solids, and solid films. Solid samples must have a substantially flat surface to ensure solid contact between the flat probe surface and the test material. The coaxial reflectance method is not recommended for powdered or crystalline solids due to irreproducible and poor contact between the probe surface and the test material. Solid materials with high dielectric loss are also not measured well using the reflectance probe method due to precision error and sensitivity of the measurement to slight variations in the integrity of probe contact/pressure with the test material.[0092]
The instrument is calibrated for each set of measurements using ambient air, a short (circuit), and deionized Water (25° C.). Water is then re-measured to check the calibration and the resultant dielectric constant must measure between 79 and 80 across the range 600 kHz to 2.9 GHz. Specifically, an HP 8752C (300 kHz to 3 GHz) and HP 8720D (50 MHz to 20 GHz) Radio Frequency (RF) Network Analyzers, and an HP 85070B Reflectance Dielectric Probe have been used for dielectric determinations. Once calibrated, these instruments are used to directly measure dielectric constant, and dielectric loss factor. From this information, calculations can be made for a number of material properties, including electric modulus, power dissipation factor (loss tangent), half power penetration depth, and reciprocal half power penetration depth. These parameters, and others mentioned herein, can be used to study the dielectric properties of materials.[0093]
The Network Analyzer/reflectance probe measurement determines the real (ε′)and imaginary(ε″)parts of the complex relative permittivity(ε
[0094]r)of a sample. The Network Analyzer measures the reflection coefficient of the MUT (Material Under Test), and an internal model in the microprocessor converts the reflection coefficient to the permittivity. The dielectric error sources include probe model accuracy (3% to 5%) and uncertainty due to the accuracy of the calibration method. The complex relative permittivity describes the interaction of a material with an applied electric field. The dielectric constant(κ)is equivalent to the complex relative permittivity (ε
r) by the relationship
where ε[0095]ris the complex relative permittivity,
ε[0096]0is the permittivity in free space (i.e., 8.854×10−12Farad/m)
The real part of the complex permittivity(ε′)as measured is proportional to the dielectric constant (κ) and is a measure of the energy stored in a material when an electric field is applied across that material. This value is greater than 1 for most solids and liquids. The imaginary part of the complex permittivity(ε″) is called the loss factor. It is a measure of how much energy is lost from a material when an electric field is applied across that material. This value is always greater than 0 as all materials have some loss under normal conditions. The loss factor includes the effects of conductivity of the material as well as its dielectric loss.[0097]
Computational Methods for Dielectric Measurements[0098]
As noted, the measured value of ε′ is most often referred to as the dielectric constant, while the measurement of ε″ is denoted as the dielectric loss factor. These are measured directly using the Network Analyzer as the Real[Permittivity] and Imaginary[Permittivity], respectively. By definition, ε″ is always positive, and a value of less than zero is occasionally observed when ε″ is near zero due to the measurement error of the analyzer.[0099]
The loss tangent or power dissipation factor is defined as the calculated ratio of ε″/ε′. This loss tangent results as the vector sum of the orthogonal real(ε′)and imaginary (ε″) parts of the complex relative permittivity (ε
[0100]r)of a sample. The vector sum of the real and imaginary vectors creates an angle (δ) where tan δ is the analytical geometry equivalent to the ratio of ε″/
68 ′. Thus the following relationship holds
where D is the power dissipation factor, and[0101]
Q is the power quality factor (often referred to in the literature)[0102]
Multiple dielectric mechanisms can contribute to the complex relative permittivity (ε[0103]r)of a sample. These include: dielectric constant, dielectric loss, conductivity, and various polarization effects. The sample thickness, temperature, density, homogeneity, and the like will also affect the measured dielectric properties of a material under test (MUT). An abrupt increase in dielectric loss for an MUT at a region over the measured frequency range indicates the occurrence of a dielectric transition. For example, in the microwave region near 1 GHz the dipolar or rotational mechanism of molecules resonates with the applied field; in the infrared region near 103GHz the molecular vibrational mechanisms resonate with the applied field; and in the visible and ultraviolet regions near 106GHz the electronic transitions resonate with an applied field. The imaginary part of the complex permittivity(ε″) or the loss factor exhibits an increase in value at each resonance transition. The real part of the complex permittivity (ε′) is orthogonal to the imaginary part and thus exhibits a decrease in value at the resonance points. These transitions can be measured and recorded for each MUT. For measurements in the microwave region, an abrupt increase in the loss factor indicates a resonance frequency where rotational energy is maximized relative to the applied field. Thus the application of an energy field at this frequency would contribute to the maximum rotational energy and resultant conformational changes and heating.
The application of the mathematical relationships and measurements discussed allows an estimation of the microwave affinity or microwave-receptivity for a particular material subjected to a microwave field. An estimation of the absorbed power and heating rate for any MUT provides information relative to selection of optimum microwave field strengths for broad applications. Selecting materials based on heating rates and required microwave power provides guidance for the composition and macro-structures of materials designed with specific microwave absorption properties.[0104]
Examples of materials that may be suitable energy receptive additives, followed by their dielectric constants are: titanium dioxide (110), hydrogen peroxide at 0° C. (84.2), water at 20° C. (80.4), methyl alcohol at −80° C. (56.6), glycerol at 25° C. (42.5), titanium oxide (40-50), gylcol at 25° C. (37), sorbitol at 80° C. (33.5), ethanol at 25° C. (24.3), propanol at 80° C. (20.1), ferrous sulfate at 14° C. (14.2), ferrous oxide at 15.5° C. (14.2), calcium superphosphate (14-15), zircon (12), graphite or high density carbon black (12-15), calcium oxide granules (11.8), barium sulfate at 15.5° C. (11.4), ruby (11.3), silver chloride (11.2), silicon (11-12), hydrogenated castor oil at 27° C. (10.3), magnesium oxide (9.7), alumina (9.3-11.5), anhydrous sodium carbonate (8.4), calcite (8), mica (7), dolomite (6.8-8). Other examples include, but are not limited to, various mixed valent oxides such as magnetite (Fe[0126]3O4), nickel oxide (NiO) and such; ferrite, tin oxide, carbon, carbon black and graphite; sulfide semiconductors such as FeS2, CuFeS2; silicon carbide; various metal powders such as aluminum, iron and the like; various hydrated salts and other salts, such as calcium chloride dihydrate; diatomaceous earth; adipic acids; aliphatic polyesters e.g.polybutylene succinate and poly(butylene succinate-co-adipate), polymers and co-polymers of polylactic acid, polymers such as PEO and copolymers of PEO, including PEO grafted with polar acrylates; various hygroscopic or water absorbing materials or more generally polymers or copolymers or non-polymers with many sites with —OH groups; other inorganic microwave absorbers including aluminum hydroxide, zinc oxide, barium titanate and other organic absorbers such as polymers containing ester, aldehyde, ketone, isocyanate, phenol, nitrile, carboxyl, vinylidene chloride, ethylene oxide, methylene oxide, epoxy, amine groups, polypyrroles, polyanilines, polyalkylthiophenes and mixtures thereof.